CN1242594A

CN1242594A - Method for implanting negative hydrogen ion and implanting apparatus

Info

Publication number: CN1242594A
Application number: CN 99110936
Authority: CN
Inventors: 三宅浩二; 林司; 桑原创
Original assignee: Nissin Electric Co Ltd
Current assignee: Nissin Electric Co Ltd
Priority date: 1998-06-12
Filing date: 1999-06-26
Publication date: 2000-01-26
Anticipated expiration: 2019-06-26
Also published as: CN1169191C

Abstract

A method for implanting negative hydrogen ions includes the following steps. Plasma containing hydrogen is generated. Negative hydrogen ions are generated in the plasma. An electric field is formed between the plasma and a substrate. Negative hydrogen ions from the plasma is accelerated by using the electric field so as to implant negative hydrogen ions into a predetermined depth of a substrate.

Description

Method for implanting negative hydrogen ions and implantation equipment

The present invention relates to a method and an implantation apparatus for implanting hydrogen ions to a predetermined depth of the entire substrate made of a semiconductor such as Si, an insulating material made of SiC, glass, or plastic, or a metal.

The purpose of implanting hydrogen ions is two. One is to form a weak porous layer (void layer) in the substrate by implanting hydrogen ions for dividing the substrate. Another object is to improve the physical properties of the desired workpiece. The different purposes of hydrogen implantation will be described below.

[1. implantation of Hydrogen ions for manufacturing SOI substrate]

An SOI (silicon on insulator) substrate is a substrate having single crystal silicon on an insulating layer thereof. Part of the SOI substrate has a thick insulating substrate (Si/insulating substrate) on which Si is disposed. For example, a structure is known in which a Si thin film is formed on sapphire. However, heterogeneous growth on different crystals often results in crystal defects. Cleavage cannot be employed, so cost reduction is impossible. Therefore, the main part of the SOI substrate is a three-layer structure whose base body is composed of silicon in which there are a thin insulating layer and single crystal silicon (Si/insulating layer/Si substrate), the insulating layer being SiO₂. That is, the three-layer structure is (Si/SiO)₂a/Si substrate).

The Si wafer is a low-cost wafer, and a high-quality silicon wafer is easily obtained. Since the SOI substrate has a structure in which Si is formed on Si, the lattice constant is the same, and the number of defects is small. Due to the cleavage, device separation is easy. To manufacture the above substrate, the internal porous layer is formed by implanting hydrogen ions. Then, another Si wafer is bonded, division is performed at the porous layer, and then the surface is polished, thereby manufacturing an SOI. The above method will be described later.

[2. manufacture of Single Crystal Si/glass substrate by implanting Hydrogen ions]

A substrate for a liquid crystal device incorporates a plurality of thin film transistors fabricated on amorphous silicon (a-Si) on a glass plate. Although the above structure is an essential part of the above substrate, the mobility of carriers in a-Si is too low to achieve high-speed operation. The substrates currently used for liquid crystal devices having the highest performance incorporate a thin polysilicon film (p-Si) formed on a glass substrate. Since the electron mobility is superior to a-Si, a high operation speed can be achieved. For example, "Low-temperature polysilicon TFT-LCD" written by Takashi Itoga, Masataka Ito and Hiroshi Takato, which is published by Technical Report of Sharp Corporation, volume 69, page 64 (1997), proposes the above-mentioned structure.

However, the above-described techniques cannot achieve satisfactory results. The polycrystals have many grain boundaries, which cause frequent scattering of electrons. The electron mobility is not satisfactory compared to single crystal Si. Since electrons are scattered due to the presence of various grain boundary levels in the grain boundaries of polycrystalline silicon, attempts have been made to reduce the grain boundary levels by implanting a hydrogen ion beam. For example,

(2) one proposal is proposed in Japanese patent laid-open No. 8-97432 entitled "Method of Manufacturing Thin-Film semiconductor apparatus by Nobuaki Suzuki". According to the above disclosure, when annealing is performed by implanting hydrogen ions, hydrogen terminates Si at grain boundaries. Therefore, the level can be lowered, thus improving mobility.

However, polycrystalline thin Si films have another problem in addition to low mobility. Since current easily flows along grain boundaries of the poly-Si, a large leakage current flows between the source and the drain. Therefore, a complicated LDD structure is required. As a result, it is impossible to realize the intended SOG (system on glass). With SOI, hydrogen is implanted into Si to form porous silicon, which is bonded to a glass plate. Then, the Si substrate is divided from the porous layer to bond the single crystal thin Si film to the substrate. Since the substrate is made of glass instead of Si, a void dicing method similar to that for manufacturing SOI can be employed. Therefore, a method of implanting hydrogen into a Si wafer to form a weak layer for bonding to a glass plate can also be employed. The Si layer is then separated very thinly to produce a single crystal Si/oxide/glass layer structure.

[3. modification of solar cell]

In a solar cell that generates electric power using silicon, single crystal silicon, polycrystalline silicon, amorphous silicon, and the like are mainly used at present. Amorphous silicon is inexpensive, but its photoelectric conversion efficiency is low (about 8%). On the other hand, the photoelectric conversion efficiency of single crystal and polycrystalline silicon can reach 15-20%. Therefore, the latter is mainly employed.

Single crystal or polycrystalline silicon solar cells are cut like a semiconductor substrate. Thus, the thickness of a single crystal or polycrystalline silicon solar cell should be 500-600 microns per wafer. A large portion of one sheet is wasted. In order to achieve a photoelectric conversion efficiency of 15 to 20%, a thickness of several micrometers to 20 micrometers is sufficient. Therefore, a cutting method of a void by hydrogen ion implantation is used. There are the following two methods.

(1) The hole cutting is performed by injecting hydrogen atoms to a depth of several micrometers by using an acceleration energy of several hundred KeV to several MeV.

(2) Hydrogen atoms are implanted to a depth of several tens of nm to several micrometers, and void cutting is performed. Before or after the cavity cut, the insufficient film thickness is compensated by epitaxial growth.

[4. implantation of Hydrogen ions into SiC]

A method has been proposed with which a similar void cutting method is used to fabricate thin SiC films. SiC is a semiconductor that can withstand high temperatures and can be used for another purpose. This proposal proposes a method for manufacturing a thin SiC film by a method similar to the method for manufacturing an SOI by forming a porous layer into which hydrogen ions have been implanted and performing exfoliation.

(4) A prior article on lecture draft of 45 th related Association, "Thin-film delay by implantation H⁺and Application of Thin-film deletion to SiC ", 29a-k-2, page 803 (1998). Naturally, any substrate having a satisfactory quality has not yet been manufactured. No device is implemented. However, various attempts have been made.

It is well known that Si-on-insulator substrates (so-called SOI substrates) incorporating a single crystal Si semiconductor layer formed on an insulating material have many advantages, for example, allowing high density integration with the ability to fabricate high speed devices, as compared to conventional bulk Si substrate structures. Therefore, many factories are actively researched and developed. The above advantages are disclosed in the following documents, for example.

(5) Special Issue: "Single-Crystal silicon on non-Single-Crystal instruments" is edited by G.W. Cullen, Journal of Crystal Growth, Vol.63, No. 3, p.429-590 (1983).

There are two methods that can be used to fabricate SOI substrates. One method is a method of forming a silicon oxide layer by direct implantation of oxygen ions (SIMOX). Another method is a bonding manufacturing method by implanting hydrogen ions, which is called a void cutting method or a new cutting method. Since the present invention relates to a method of implanting hydrogen ions in a wafer, the novel dicing method can be improved.

Methods for fabricating SOI substrates using novel dicing methods are disclosed, for example, in

(6)“Smart-Cut：A New silicon on substrate technology based on hydrogen generation and wafer bonding ", Jpn. J appl. Phys, Vol.36 (1997), p.1636-. Numerous other documents have been published. These methods will be briefly described below. Oxidizing the surface of the first Si substrate to form SiO₂And (3) a membrane. Then, at 1 × 10¹⁴/cm²Or more, at about 100 KeV. Thus forming a porous layer having a large porosity to a depth of about 0.2 to 0.5 microns. A heat treatment is then performed to recover the damage of the surface Si layer caused by the implantation. Then, the first Si substrate is bonded. The second Si wafer may be provided with an insulating layer thereon. A shear force is applied in a vertical direction to cut the first substrate at the porous layer. Then, the surface is polished, thereby manufacturing an SOI substrate.

The gas that has to be injected can be a noble gas or nitrogen as a substitute for hydrogen. Hydrogen is the most preferred gas. The reason is that hydrogen with a small mass can be deeply injected. In addition, hydrogen does not seriously damage the Si layer surface.

The most commonly used method of implanting hydrogen ions utilizes an ion implantation apparatus for implanting impurities B or P. Fig. 1 illustrates a method of implanting hydrogen ions using a typical ion implantation apparatus.

Plasma is excited using a hot filament, microwave or high frequency. I.e. devices using filament excitation. A process chamber 1 having a pressure that can be reduced to a vacuum level is provided with a filament 2. The taps of the filament 2 are led out to the outside through the insulating portions 5. A DC filament power supply 3 is connected to both ends of the tap. The process chamber 1 has a gas inlet 4 so that hydrogen can be supplied. An arc power supply 6(Vak) is connected between the chamber 1 and the filament 2. An acceleration power supply 7(Vacc) is provided between the negative electrode of the arc power supply 6 and the ground. The potential of the processing chamber 1 is Vacc + Vak.

Three electrodes each having one hole are provided on the outside of the outlet 8 of the process chamber 1 so that the axis of the opening portion is common to each portion. These electrodes are an accelerating electrode 9, a decelerating electrode 10 and a ground electrode 11. The negative pole of the acceleration power supply 7 is connected to the acceleration electrode 9 via a resistor 13. The retarding power supply 12 is connected to the retarding power supply 10. A quarter-arc mass separation magnet 14 is provided atChamber outlet 8 and extensions of

electrodes

9, 10 and 11. The ion beams 15 emitted by the process chamber 1 are introduced into the mass separating magnet 14 through the inlet 16 so that they draw a curved trajectory under the action of the magnetic field. Then, the ion beam 15 is released from the exit 17. Since the trajectory has been adjusted according to mass and energy, the monoatomic ion H⁺May pass through the central track 26 so as to pass through the slit plate 18. On the other hand, diatomic H₂ ⁺An eccentric locus 27 is drawn and then collides with the wall of the mass separating magnet 14 and the slit. Then diatomic H₂ ⁺And (6) dissipating. A positive hydrogen atom ion H⁺May pass through the slit plate 18 and then be scanned laterally by a scanning mechanism 22 consisting of the

counter electrodes

19 and 20 and a variable power supply 21. The scanned beam 23 is implanted into a Si wafer 24 disposed on a susceptor 25.

Various types of positive ions are generated in the hydrogen plasma. If multiple types of positive hydrogen ions are implanted, undesirable multiple hydrogen implanted layers may be formed. Therefore, only one type of hydrogen positive ion must be selected and implanted. For selective implantation, a mass separation must be performed. For mass separation, the diameter of the beam may be reduced. I.e. a beam much smaller than the wafer diameter is required. Since each beam has a smaller diameter than the wafer, such a beam cannot implant the entire surface of the wafer at once. Therefore, a scanning mechanism that oscillates the beam is required. The presence of the mass separation structure and the scanning mechanism can create various problems.

The methods of mass separation, scanning, and hydrogen ion beam implantation using the ion implantation apparatus are similar to those of the conventional impurity ion implantation apparatus. It is easy to estimate that such a device is an expensive and complex device. Since a magnet having a large height must be provided, a large area is required for installation. Since scanning with the beam must be performed to perform implantation, a long processing time is required per wafer. Therefore, the yield is too low to reduce the cost per SOI substrate. The above fact is why it has been recognized that advantageous SOI substrates cannot be widely used.

In recent years, another method has been proposed, by which a substrate is exposed to hydrogen plasma, and a negative pulse voltage is periodically applied to the substrate so as to implant hydrogen ions over the entire substrate surface. The above methods are disclosed in the following documents.

(7) "Ion-cut silicon-on-insulating polymerization with plasma polymerization," edited by Xing Lu S.Sundar Kumar Iyer et al, appl.Phys.Lett.71(19), 1997.

Fig. 9 illustrates the above technique. Hydrogen gas is supplied to the plasma chamber 200 through the rawmaterial gas inlet 202. The microwave 204 generated by a magnetron (not shown) and transmitted in the waveguide 203 is supplied to the plasma chamber 200. A Si wafer 207 is disposed on a pedestal 208 in the plasma chamber 200. The base 208 is supported by a shaft 209. The shaft 209 is negatively biased by a negative bias supply 220. The wafer 207 is contacted with the plasma 206. When the wafer is negatively biased, the hydrogen positive ions H⁺And H₂ ⁺One implant into the entire surface of the wafer.

The above method does not require mass separation, and thus can simplify the structure. The above fact has no advantage. All positive ions (H) in the plasma are positive ions (H) since no mass separation mechanism is required₂ ⁺And H⁺) Is introduced into the wafer, which is undesirable. As a result, two porous layers each having a large porosity are formed. In this case, the new dicing of the wafer cannot be satisfactorily performed. Due to the molecule (H)₂) The mass of (c) and the mass of the atom (H) are different from each other by two times, so that light H is added with the same acceleration energy⁺The depth of ion implantation is heavy H₂ ⁺Twice the depth of implantation. The first layer is composed of H₂ ⁺Formed of H as the porous layer of the second layer⁺And (4) forming.

Must be avoided in the field of reactions involving monoatomic ions H⁺And cutting the formed second layer. The reason is that the first layer remains on the SOI substrate when the SOI is manufactured by bonding to another wafer. If the entire surface of the first layer more adjacent to the surface is allowed to separate (the porous layer is made of H)₂ ⁺Made) no problem occurs. If there is a partial cut in the second layer, surface defects may be generated, resulting in a great reduction in manufacturing yield.

In the above document, the plasma state is controlled so that the proportion of positive ions in the plasma is H by optimizing the gas flow rate and the applied power source₂ ⁺/H⁺90: 10, thereby overcoming the above-mentioned problems. I.e. H₂ ⁺Is implanted at a high rate. Due to monoatomic ions H⁺Is small and the thickness of the first layer is reduced. Thus, a method is used to facilitate the separation to occur in the first layer.

However, H cannot be completely removed⁺. Therefore, there is a risk that separation occurs in the second layer. The conventional method cannot generate any of molecular ions/atomic ions in the plasma with priority given to the fact that other ions can be ignored. If the plasma parameters are shifted even by a small amount, positive ions H will be present₂ ⁺∶H⁺The ratio of (a) to (b) is changed. In particular, the key issue is the inability to ensure the safety of the manufacturing equipment.

In the preferential implantation of molecular ions H₂ ⁺When the porous layer is formed, H₂ ⁺It needs to be about H⁺The implant is to a voltage twice that required for the required depth. Therefore, technical difficulty in providing a power source of plasma voltage increases. In addition, the cost is also increased. Therefore, a mass separation mechanism is required.

A key problem with the first approach is the need for mass separation. In the plasma, hydrogen is dissociated as described aboveSub-comprises H⁺And H₂ ⁺Two kinds of ions. If only one is implanted, the porous layer is disappointingly formed as a multilayer structure. The ion implantation apparatus shown in fig. 1 is provided with a mass separation system for uniquely selecting an ion beam. Since a large magnet is required, the size and cost of the apparatus cannot be reduced. The diameter of the ion beam is reduced because the mass of the coarse beam cannot be sputtered. Since the diameter of the ion beam is reduced, ions cannot be implanted over the entire surface of the wafer at once. Therefore, a scanning mechanism must be provided in order to scan the entire surface of the wafer with the beam.

The method of exposing a substrate to a hydrogen plasma and applying a positive plasma voltage to the substrate to implant hydrogen ions (see fig. 9) solves the above-mentioned problem by controlling plasma parameters (see fig. 9). However, the above method is incomplete. That is, the problem of implanting a plurality of hydrogen positive ions must be solved.

A primary object of the present invention is to provide a method and apparatus for implanting hydrogen ions in a semiconductor substrate, an insulating substrate, or a metal substrate so as to confine ions generated from hydrogen to one kind.

It is another object of the present invention to provide an apparatus for implanting hydrogen ions to confine generated ions to one type, which can eliminate the need for mass separation, and can reduce the cost and the required installation area.

It is still another object of the present invention to provide an apparatus for implanting hydrogen ions, which does not require scanning with the hydrogen ions since the generated ions are limited to one type, thus improving the yield.

As mentioned above, the hydrogen cations include various types, such as H⁺And H₂ ⁺. Therefore, it is not easy to generate one type of ions at a ratio of 80% or more. If mass separation is performed, it is impossible to reduce the size of the apparatus and reduce the cost thereof. At worst, the yield is low and disappointing. Therefore, the present invention does not employ the above-described method.

According to the present invention, a method of implanting hydrogen anions includes the steps of: generating plasma-containing hydrogen; generating hydride ions in the plasma; forming an electric field between the plasma and the substrate; and accelerating the hydrogen negative ions from the plasma by using the electric field to implant the hydrogen positive ions at a predetermined depth of the substrate.

According to the present invention, an apparatus for implanting hydrogen negative ions comprises: a hydrogen generating device for generating plasma-containing hydrogen; a negative hydrogen ion generator for generating negative hydrogen ions in the plasma; and electric field forming means for forming an electric field between the plasma and the substrate; wherein the negative hydrogen ions from the plasma are accelerated by the electric field to implant the negative hydrogen ions to a predetermined depth of the substrate.

In the drawings:

FIG. 1 is a schematic sectional view showing a conventional apparatus for implanting hydrogen positive ions into a Si wafer;

FIG. 2 is a schematic cross-sectional view of a first embodiment of the present invention configured to generate hydrogen plasma by high-frequency excitation and to apply a positive bias voltage for a time period during which negative ions are temporarily added after interruption of the high-frequency power supply to implant hydrogen negative ions into a Si wafer;

FIGS. 3A and 3B are graphs showing pulse waveforms showing a timing of applying a high frequency power source and a timing of applying a positive bias voltage to a wafer in the first embodiment shown in FIG. 2;

FIG. 4 is a sectional view showing an apparatus of a second embodiment in which hydride ions are implanted into a wafer by dividing plasma into two parts by forming a magnetic field in the middle portion of a process chamber by supplying current to a conductive rod using an ECR plasma method to improve the efficiency of generating the negative ions;

FIG. 5 is a sectional view showing an apparatus of a third embodiment in which hydride ions are implanted into a wafer by dividing plasma into two parts by forming a magnetic field in the middle portion of a process chamber by supplying current to a conductive rod using an ECR plasma method to improve the efficiency of generating the anions;

FIG. 6 is a sectional view showing an apparatus for implanting hydride ions into a wafer by the ECR plasma method according to a fourth embodiment;

FIG. 7 is a sectional view showing a fifth embodiment configured to employ a sputtering type negative ion source for implanting hydrogen negative ions into a wafer;

fig. 8 is a diagram showing a process for manufacturing an SOI substrate, which includes implanting hydrogen negative ions into a Si substrate to form a hydrogen porous layer, and then may attach other Si to remove Si from the porous layer;

fig. 9 is a sectional view showing a conventional method for implanting hydrogen positive ions over the entire surface at once;

FIG. 10 is a sectional view showing an apparatus for generating a magnetic field in the middle portion of a process chamber by using a current on a conductive rod and by ECR plasma method to divide plasma into two parts and thereby increase the proportion of generated negative ions, thereby extracting a negative ion beam by an extraction electrode system and implanting hydrogen negative ions into a wafer, according to a sixth embodiment;

FIG. 11 is a sectional view showing an apparatus of a seventh embodiment configured to adopt an ECR plasma method to form a magnetic field in an intermediate portion of a process chamber by using a magnetic field generated by a permanent magnet to divide plasma into two parts and to increase the proportion of generated negative ions, thereby extracting a negative ion beam by using an extraction electrode system and implanting hydrogen negative ions into a wafer;

FIG. 12 is a cross-sectional view showing an eighth embodiment of the present invention, which utilizes a sputtering type negative ion source using Cs to implant negative hydrogen ions into a wafer;

fig. 13 is a sectional view showing an apparatus for generating hydrogen plasma by excitation with microwaves and oscillation absorption of microwaves by using a magnetic field generated by a coil to temporarily interrupt introduction of electrons from a microwave source, and applying a voltage to an extraction electrode system for extracting a negative ion beam for a short time after the interruption in which negative ions increase to implant hydrogen negative ions into a Si wafer according to a ninth embodiment of the present invention.

The present invention will be described in detail below.

In the present invention, the hydride H^-For replacing the positive ions. Only H^-Is a stable hydride ion. If molecular anions such as H are generated₂ ^-The lifetime of the above ions is short, only a few ns to a few tens of ns. Thus, the ions are rapidly separated into H and H^-. Therefore, the hydride ion is 100% H^-. For example, H in hydride is disclosed in the following documents^-The unity of (A):

(8) "Ion Source Engineering," written by Junzo Ishikawa, published by Ionics, pages 34-35.

The invention utilizes H in negative ions^-Significant singleness of. A substrate made of Si, a dielectric substrate, or a substrate made of glass, which must be processed, is placed in a plasma chamber and brought into plasma contact. Then, in the form of pulsesPositive pressure is applied to the substrate and the susceptor to be treated so that monatomic hydrogen anions H^-Concentrated implantation into the substrate. The substrate is previously brought into contact with plasma, and then hydrogen ions are collectively implanted into the entire substrate. A thin discontinuous potential layer, a so-called space charge layer, is present between the plasma and the substrate. An accelerating voltage is applied to the space charge layer to accelerate H^-Ions.

No mass separation is required due to the absence of other hydride ions. Since the substrate is disposed in the plasma chamber and then brought into contact with the plasma, beam scanning is not performed, nor is beam scanning required. Since the concentrated implantation is performed, a high yield can be achieved. The above facts are an essential part of the present invention.

Due to only a single atom and a monovalent H^-Is present in hydride ions, so no mass separation is required. Thus, large and heavy mass-separating magnets are not required. Therefore, the size of the apparatus can be reduced, and the area required for installation can be reduced. Since a magnet is not required, the cost can be reduced.

Since no mass separation is required, it is not necessary to form a beamlet. The substrate is directly disposed in the plasma, so the substrate may be previously brought into contact with the plasma. Then, a positive voltage is applied in a pulsed manner to implant hydrogen negative ions into the substrate. Since beam scanning is not performed, the cost of the apparatus can be reduced by an amount corresponding to the cost of the scanning mechanism. Since no scanning mechanism is required, a scanning distance is not required, and the area required for mounting the apparatus can be reduced. Since the ion implantation can be performed in a concentrated manner, the time required for completing the implantation process can be greatly shortened, and the yield can be greatly improved. In addition, the cost of manufacturing the SiSOI substrate by the void dicing method can be reduced.

It should be noted that the present invention, which employs hydride beam implantation, has a problem. That is, a method for generating a large amount of hydride ions is required. The reason why all the conventional techniques employ positive hydrogen ions which must be implanted is that positive ions are easily generated. Negative ions are not easily generated. Since there is an electrically neutral condition, the number of positive ions is equal to the number of electrons + negative ions. In the plasma, the number of negative ions is always smaller than the number of positive ions. Since both negative ions and electrons are negatively charged particles, there arises a problem that electrons are also injected when negative ions are injected by making the ion source in a negative state. The required ion current is wasted after the electrons are injected into the substrate. In addition, there is a problem that the substrate is heated by electrons, which is undesirable. The main part of the ion implantation apparatus employs positive ions because the positive ions are easily generated and the mixing of electrons can be prevented.

Some solutions may solve the problem of difficulty in generating negative ions. One solution is to rapidly blank electrons while maintaining a neutral state in the plasma to temporarily add negative ions. If a transition to a monovalent ion is made, the number of electrons + the number of negative ions is equal to the number of positive ions. Therefore, when the number of electrons temporarily becomes closer to zero, the number of negative ions may be closer to the number of positive ions. When the plasma excitation device is interrupted, the electron temperature rapidly decreases when the plasma excitation device is turned on. So low-energy electrons increase.

Low-energy electrons having a large cross-sectional area and being easily bonded collide with neutral atoms and molecules at the time of collision. The low-energy electron having collided with the neutral hydrogen atom is trapped by the neutral hydrogen atom, so that the low-energy electron becomes monovalent H^-. Collisions with neutral hydrogen molecules cause the molecules to split into two atoms with a certain charge. Thereby generating neutral atoms and negative ions H^-. When the plasma is blanked as described above, electrons are rapidly decreased, and negative ions are increased. Naturally, the above phenomenon occurs temporarily. Then both positive and negative ions later begin to decrease. In the above short time, a bias voltage is applied to the substrate (wafer) and the susceptor to implant negative ions into the wafer.

Since the implantation is performed in a short time, repeated implantation must be performed. Thus, the plasma is pulsed on/off and then after a predetermined time delay, the wafer and susceptor are pulsed. Although the amount of ions implanted per time is small, a desired dose can be obtained due to repeated implantation operations. The above method is temporarily referred to as a "post-cut positive pulse method".

In addition to the post-cut-off positive pulse method, another method for densely generating negative ions is known. Electrons in the plasma have a high temperature and a high energy of several tens of eV. Therefore, it is not easily bonded to a neutral atom. Low-velocity electrons having energies of about 0.1eV to about 0.01eV readily combine with neutral atoms, allowing the generation of negative ions. Therefore, the above method has a step of lowering the electron energy to about 0.1eV or less to enlarge the cross-sectional area of collision and bonding with neutral atoms and neutral molecules. The above method is called "energy filtration method". The above method is a method of increasing the density of negative ions in terms of the time taken and the space occupied by the negative ions. The above method can be employed simultaneously with the post-cut positive pulse method.

There is a method of generating negative ions by utilizing the fact that Cs has a low work function. The above-mentioned methods are known methods. That is, Cs is allowed to adhere to a target that is positively biased in advance, and then neutral atoms and molecules collide with Cs. The Cs atoms then move toward neutral atoms and molecules to generate negative ions. Although Cs is made positive, Cs can be restored to a neutral state because electrons are transferred from the target. The above method skillfully adopts the fact that Cs is easy to release electrons (has a low work function). It should be noted that Rb may be substituted for Cs. The above method can be used with a post-cut positive pulse method.

The method of generating plasma includes a plurality of methods, which are an arc discharge method using a filament, a high-frequency discharge method between a parallel plate and a flat plate electrode, a DC discharge method, a microwave discharge method, and a method of generating sputtering negative ions. The ion sources are present in an amount corresponding to the excitation means described above. The invention can be used for any of the post-cut positive pulse method sources.

Although hydrogen gas is the most suitable raw material gas, the raw material gas is not limited thereto. As an alternative to the raw material gas, hydrogen + a rare gas may be used. The rare gas may be, for example, helium and argon. The above gas is stable in a plasma state, allowing hydrogen anions to be generated when the rare gas and hydrogen collide with each other. Therefore, the density of negative ions can be further increased.

As a substitute for the raw material, hydrogen-containing compounds can also be usedType of gas, e.g. SiH₄Or CH₄Used as raw material gas. In the presence of SiH₄Then, remove H^-In addition, SixHy ions are also generated. Additional ions, which are very heavy ions, are simply implanted into locations near the substrate surface. Therefore, the ions are easily removed by polishing.

In the present invention, a positive voltage is applied to a wafer disposed in contact with plasma, and then hydride H is applied^-And implanting into a Si substrate, a glass substrate or a dielectric substrate. Since the main plasma of hydride is H^-Therefore, mass separation is not required. Since the reduction of the diameter of the beam for mass separation is avoided, a scanning device is not required, and therefore, the device can be simplified, the device size can be reduced, and the yield can be improved. A method of generating negative ions that are not easily generated is described below.

[1. post-cut positive pulse method]

(post-cut negative ion Beam method)

The plasma is switched on in a pulsed manner. Immediately after the plasma is turned off, a positive voltage is applied to the substrate (wafer) in a pulsed manner so as to implant negative ions (in this method, the plasma is turned on in a pulsed manner, and a predetermined voltage is applied to the extraction electrode system immediately after the plasma is turned off so as to implant negative ions).

When the plasma generator is turned on, a hydrogen-containing plasma is generated in the plasma generation chamber. The plasma generating device is switched off. The electron temperature in the plasma is then rapidly reduced from a few tens of eV to 5-7eV within a few microseconds. On the other hand, the density of electrons and positive and negative ions does not substantially change during the above time period, and low-energy electrons become dominant in the plasma. Since the low-speed electrons and hydrogen molecules undergo dissociative adhesion, the possibility of hydride generation rapidly increases. The above facts are easily represented by the formula " "and" "means. Since the adhesion occurs, the density of neutral atoms rapidly increases immediately after the plasma generator is turned off. After a 20-30 microsecond time period, is light materialThe electrons of (2) diffuse rapidly, and thusIs blanked. The density is then reduced. Positive and negative ions having a large mass are not substantially blanked. Thus, an unusual plasma is generated, (essentially electron free), with a very large electron density, where positive and negative ions sustain the plasma. The above phenomenon is disclosed in, for example, the following documents.

(9) Seiji Samukawa, "desk Modulated Plasma", Applied Physics, Vol.66, No. 6, 550-558 (1997).

(10) Hopkins, M,. Bacal&w.g.graham, "Enhanced volume production of negative ions in the post discharge of a multicusp hydrogen discharge", j.appl.phys.70(4), page 2009-.

Document (9) discloses a plasma of chlorine and argon. Document (10) discloses the result of detecting hydrogen plasma. The inventor skillfully adopts the technology. A state in which the negative ion density is high is realized in a short time after the plasma is cut off. The present invention has a step of applying a positive pulse voltage to a substrate, i.e., a susceptor, immediately after forming an unusualplasma (when the number of positive ions is negative). As a result, hydride (H)^-) Implanted to the entire surface of the Si substrate.

[2. energy Filter method]

The plasma chamber is divided into two chambers. A raw material gas is introduced into a first plasma chamber to be excited to generate plasma. In the second plasma chamber, a wafer and a susceptor are disposed. An energy filter realized by a magnetic field is formed between the two plasma chambers. In the first plasma chamber, the generation of plasma is strongly performed so that electrons have high energy. The energy filter inhibits the passage of high-energy electrons. In the second plasma chamber, a large number of low energy electrons are present. Low-energy electrons have a large cross-sectional area for collision and bonding with neutral molecules and atoms. The low-energy electrons are combined with neutral atoms, and the neutral atoms are converted into negative ions H^-. As described above, low energy electrons are introduced from the first plasma chamber after the amount of low energy electrons is reduced. The energy filter is selective to electron energy. It should be noted that neutral atoms and molecules are allowed to pass freely. This is achieved by forming a mold havingMagnetic fields of several tens of gauss strength. The magnetic field may be formed by oppositely disposing permanent magnets. With regard to an alternative method, the magnetic field may be formed by passing a current through a plurality of parallel conductive rods.

[3.Cs method]

The Cs method is a widely used method in which Cs is used as a negative ion source. When Cs is adsorbed to the surface of the metal material, Cs has an effect of lowering the work function of the surface of the metal material. Due to the lowering of the work function, electrons are easily discharged. When the metal materialis negatively biased, the metal material functions as a material for electron discharge. The hydrogen molecules and hydrogen positive ions collide with Cs, and electrons are supplied to the hydrogen molecules, etc. Thereby generating hydride ions. Solid Cs is contained in an evaporation source, and then the Cs is heated and vaporized so as to be introduced to the surface of the metal material. As the substitute for Cs, rubidium Rb, potassium K, or barium Ba may be used.

Example 1 (with increasing negative ions immediately after plasma is switched off)

Referring to fig. 2, a first embodiment will be described. The processing chamber 30 having the raw material gas introduction opening 29 is an apparatus for generating plasma by high-frequency excitation. The susceptor electrode 31 is disposed at a lower portion of the processing chamber 30, and the counter electrode 32 is disposed at an upper portion. The base electrode 31 is supported by a shaft 33. The shaft 33 is insulated from the process chamber 30 by an insulating member 34. The counter electrode 32 of the parallel plate electrodes 31 and 32 is connected to a high-frequency power supply 41 of 13.5MHz through an electric wire 37, a matching box 38, an electric wire 39 and a first switch 40. The high frequency power source 41 is triggered by the first trigger circuit 45 to be periodically turned on/off.

The Si substrate 58 is mounted on the base electrode 31 among the parallel plate electrodes 31 and 32. A shaft 33 connected to the base electrode 31 is supported by the process chamber 30 through an insulating member 34. The shaft 33 is connected to the positive pole of a positive bias power supply 44 through a wire 42 and a second switch 43. Note that the power supply described above is a positive bias power supply, i.e., not a negative bias power supply. The second switch 43 is periodically turned on/off by a second trigger circuit 46.

The timing adjustment circuit 47 turns on/off the first and second flip-

flop circuits

45 and 46 with a predetermined time delay, as shown in fig. 3A and 3B. The first switch that turns on the plasma is pulsed on/off for a short time. Immediately after this, the second switch 43, which positively biases the susceptor electrode 31 and the wafer 58, is turned on/off for a short time. The reason for this is as follows.

Hydrogen gas is introduced into plasma chamber 30. The first trigger circuit 45 opens the first switch 40 (first transition 48 of pulse). High-frequency power is applied to the counter electrode 32 and the base electrode 31. A glow discharge then occurs between these electrodes, producing a hydrogen plasma. The kinetic energy of the electrons is about several tens of eV. The above state is a state in which the plasma is turned on when the high-frequency power source 49 is turned on, as shown in fig. 3A and 3B.

When the first trigger circuit 45 is turned off (falling edge 50), the first switch 40 is closed. Whereupon the plasma begins to blank. The electron temperature drops, causing energetic electrons each having several tens of eV in the plasma to be rapidly blanked in about a few microseconds. At the same time, the energy of the electrons is lost to low energies of about several eV. If the energy is low, the velocity is reduced, and therefore, the collision cross-sectional area with hydrogen atoms is greatly increased. That is, collision with hydrogen easily occurs. Low-energy electrons can be dissociatively attached to hydrogen molecules, thereby generating H^-. Therefore, after the trigger circuit 45 is turned off 50, H^-The density of (a) rapidly increases. H as the gas pressure rises and the microwave power supplied increases to enhance the electric field^-Ions are preferentially generated. As a result, the main part of the negative ion is constituted of a monoatomic atom and monovalent H^-Ions. H cannot be generally applied although it depends on the plasma vessel and the generation conditions due to the above facts^-Has a peak in the range of several tens of microseconds to 100 milliseconds. At this time, the number of negative ions has increased to be equal to the number of positive ions. Subsequent collision with a wall surface or the like causes H^-And gradually decreases.

It is more preferable that the electron density is extremely reduced during the period from the turning on of the first flip-flop circuit 45 to the turning off thereof. During the period from the time when the first trigger circuit 45 is turned off (51) to the time when it is turned off 10 microseconds later, the second trigger circuit 46 is turned on (53). When the second trigger circuit 46 is turned on (54), a positive bias of 20KV-220KV is applied in pulses to the Si substrate. A positive bias voltage is applied to the wafer to draw negative ions in the plasma 57 onto the wafer 58 and accelerate them to a deep portion of the wafer. Since the spread of the plasma 57 is larger than the size of the wafer 58, the hydride ions are uniformly implanted over the entire surface. Therefore, no scanning is required. Although the negative ions are reduced, the positive bias is rapidly stopped (first transition 55). Therefore, waste of time can be prevented.

The next operation (first transition 48) to turn on the plasma is prevented so that the plasma is generated. Then, the plasma is blanked so that the negative ion concentration increases, and then a positive bias is applied (first transition 53). Repeating the above operation to repeat the negative ions H^-A small amount is implanted into the wafer.

In this embodiment, semiconductor switches are used for the switches 40 and 43. In the above case, it is confirmed to have a duty ratio of 1% and a repetition frequency as high asseveral Hz to 10 KHz. Note that a thyristor or the like may also be employed as the switching device.

The essential part of the first embodiment is that the plasma is switched on/off, H^-Ions are generated in large quantities during periods when the plasma is off and positive bias is applied at a desired timing to convert H^-Ions are implanted into the Si substrate. The phenomenon that negative ions increase immediately after plasma cutting is used for a skilful second.

Although a high frequency excitation device is employed, the invention is not so limited. The plasma generating means may be a microwave plasma or a DC discharge plasma instead of the high frequency plasma. In any case, the negative ions are increased immediately after the plasma generation device is turned off during the operation of periodically turning on/off the plasma generation device, at which time a positive bias voltage is applied to the wafer.

Second embodiment (passing of Low-energy electrons through energy Filter)

There are many ways to generate hydride ions in large quantities. In particular, many results have been obtained in developing a source of hydride ions for a neutral particle implantation apparatus (NBI: neutral beam implantation) used in nuclear fusion research. The second embodiment employs the above-described technique. The structure and operation of the hydride source are disclosed in the following documents.

(11) "Ion Source Engineering," page 486-492, written by Junzo Ishikawa published by Ionics.

Hydrogen is introduced into the plasma chamber, and then a heating filament disposed in the plasma is excited and heated to generate thermal electrons. A DC voltage of about 40V to 100V was used, with the heating filament as the negative electrode and the plasma chamber wall as the positive electrode. A DC discharge is then initiated to generate a hydrogen plasma. The permanent magnets are disposed outside the plasma generating chamber such that south poles and north poles are alternately disposed. A multi-pole (cusp magnetic field) magnetic field is formed to effectively confine the plasma.

The plasma chamber is divided by a magnetic field into a first plasma chamber and a second plasma chamber. When a current passes through the plurality of parallel conductive rods, a weak magnetic field of about several tens of gauss is formed. The above structure is referred to as an "energy filter". The energy filter prevents a large amount of high-energy electrons of about several tens eV generated in the first plasma chamber from being introduced into the second plasma chamber.

In the second plasma chamber, a plasma is generated containing a plurality of low energy electrons in the range of about 1eV to about 0.1 eV. Dissociatively adhering electrons to hydrogen molecules results in the generation of large quantities of H^-。

Fig. 4 shows the second embodiment in detail. The energy filter adds low energy electrons and thus enhances the production of negative ions. Although the heating filament plasma generating apparatus will be described below as an example, the present invention may be applied to another excitation method. The plasma chamber 61 introduces a gas inlet and a gas outlet (not shown). Hydrogen, argon, etc. are introduced through the gas inlet. A filament 64 may be passed through the lead-in 62 for connection to a filament power supply 65. An arc power supply 66 and a first switch 67 are disposed between the filament 64 and the plasma chamber 61. The filament 64 is heated to emit thermal electrons. The thermal electrons flow to the wall of the plasma chamber 61 to generate arc discharge. As a result of the arc discharge, the gas is excited, and a plasma is generated.

A plurality of parallel conductive rods 69 are provided in the middle portion of the plasma chamber 61. Causing current to flow in the same direction. A magnetic field of about several tens of gauss to about 100 gauss is thus formed around the conductive rod 69. High-energy electrons cannot pass the potential barrier in the form of a weak magnetic field. Low energy electrons can pass through the barrier. Thus, the magnetic field generated by the conductive rods 69 acts as an energy filter, allowing low energy electrons to selectively pass through.

The plasma chamber 61 is divided into upper and lower portions by a conductive rod 69, the upper portion is a portion where hydrogen is excited by a heating filament, and the upper portion is referred to as a first plasma chamber 68. The lower portion is a portion where negative ions are generated, and the lower portion is referred to as a second plasma chamber 70. A susceptor 73 on which a wafer 72 has been mounted is disposed in the second plasma chamber 70. The base 73 is connected to an external circuit through a shaft 74. The shaft 74 is connected to a second switch 76 and a positive bias power supply 77. The timing adjustment circuit 78 turns on/off the first switch 67 and the second switch 76 in the form of pulses in accordance with the timing shown in fig. 3A and 3B.

The positive bias is appropriately determined to cause hydrogen implantation into the Si wafer. Typically, the implant depth is achieved with about 20KeV to 220 KeV. The timing adjustment circuit 78 turns on/off the second switch 76. The wafer is biased to a positive voltage when the second switch is closed. Therefore, the negative hydrogen ions are deeply implanted. Since the wafer is disposed in the dispersed plasma, the hydride ions can be implanted all at once on the entire surface. Since the plasma has a large area, mass separation and beam scanning are not required.

A plurality of permanent magnets 71 are provided on the outer wall of the lower portion of the plasma chamber 61 so that the north and south poles of the adjacent magnets are alternately reversed. The adjacent magnets generate cusp magnetic fields to achieve the effect of confining the charged particles to the middle portion of the plasma chamber.

This operation will be described below. Hydrogen is introduced through the gas inlet. The filament causes thermal electrons to discharge, so that arc discharge occurs. As a result, the gas is excited, thereby generating plasma. The plasma contains positive ions, electrons, neutral atoms, and molecules. Although containing only a small amount of negative ions, it contains a large amount of electrons. The electrons have a high energy of about 10 eV. Since electrons are high-speed electrons, collision with neutral atoms does not easily occur.

A magnetic field B (several tens of gauss to 100 gauss) formed by the conductive rod 69 exists at the interface between the first plasma chamber 68 and the second plasma chamber 70. Charged particles, in particular high-speed electrons, cannot pass through this potential barrier in the form of a magnetic field. Neutral atoms and molecules are capable of passing through a magnetic field B. Light-weight electrons having low energy (about 1eV or less) can pass through the magnetic field B of the conductive rod 69. The low-energy electrons are trapped by the magnetic field and perform a cyclotron motion. The low-energy electrons then escape the action of the magnetic field.

Since low-energy electrons exist in the second plasma chamber 70, the low-energy electrons are dissociatively attached to neutral hydrogen molecules. As a result, hydride ions are generated. The major part of the low-energy electrons can attach to neutral atoms and molecules, so the low-energy electrons are blanked. At this time, the negative ion density is greatly increased. At this time, a positive bias is applied to the wafer 72 and the susceptor 73, and negative ions are extremely strongly attracted by electrostatic force.

In the second embodiment, hydrogen gas is supplied only to the first plasma chamber 68. The present invention is not limited thereto. Generally, the efficiency of generating negative ions increases as the pressure of hydrogen gas increases. To improve the efficiency of generating negative ions, hydrogen gas may also be provided into the second plasma chamber 70. The supply of hydrogen gas to the first plasma chamber may be prohibited and only the supply of hydrogen gas to the second plasma chamber 70 may be provided.

During forward bias off 56, the wafer is exposed to positive ions. The above state does not cause any problem. Simple contact of the positive ions does not cause their introduction into the wafer. In this embodiment, the timing adjustment circuit 78 intermittently energizes the plasma. After a short time from plasma cutoff, a positive voltage is pulsed on the wafer 72. When the density of negative ions is increased, the wafer is biased to a positive pressure, so that negative ions can be efficiently implanted into the wafer.

Third embodiment (passing of Low-energy electrons through energy Filter)

Fig. 5 shows a third embodiment. This embodiment is constructed such that the energy filter is constructed of permanent magnets 81-84, which are used in place of the conductive rods. Permanent magnets 81-84 facing in the same direction are disposed at the middle height of the plasma chamber 61, except for the permanent magnet 71 for forming the cusp magnetic field. A magnetic flux density B directed in one direction is formed between the

permanent magnets

81 and 82, and between the

permanent magnets

83 and 84. The magnetic flux density B interrupts the high-speed electrons, i.e. acts as an energyfilter. The same effect as that obtained by passing current through the collector bar structure shown in fig. 4 can be obtained. The permanent magnet 71 disposed at the lower portion generates a cusp magnetic field. When the wafer 72 is biased with intermittent positive electrical power, negative ions can be implanted similar to the embodiments described above. Since the negative ions are implanted over the entire surface at once, mass separation and beam scanning are not required.

Fourth embodiment (ECR plasma apparatus)

Fig. 4 and 5 show a heated filament plasma apparatus. Fig. 6 shows an ECR microwave plasma apparatus which performs confinement operation using a vertical magnetic field generated by an ECR coil instead of a cusp magnetic field.

The microwave 87 generated by the magnetron 85 is transmitted in the waveguide 86. The microwaves 87 pass through a dielectric material window 88. The plasma chamber 89 introduces a gas inlet (not shown) and a gas outlet (not shown) and excites the gas into a plasma using microwaves. Coil 90 is disposed around plasma chamber 89. Coil 90 generates a vertical magnetic field 92 in plasma 91 in plasma chamber 89. The electrons make a cyclotron motion under the action of the magnetic field of the coil. In a region where the frequency of the cyclotron motion is the same as the frequency of the microwave, resonance absorption (ECR) of the microwave occurs. Therefore, the density of the plasma is increased. A wafer 94 supported by a susceptor 93 is disposed in the plasma chamber 89. The entire surfaces of the plasma 91 and the wafer 94 are in contact with each other. A switch 97 and a forward bias power supply 98 are connected to the base 93. The timing adjustment circuit 99 periodically turns on/off the switch 97. After an appropriate time delay, the magnetron 85 is also turned on/off at the same timing as shown in fig. 3A and 3B.

The magnetron 85operates in a pulsed fashion. In response, the plasma is turned on. After the plasma is blanked, the density of negative ions is increased. At the same time, the wafer 94 and susceptor 93 are biased to a positive pressure. As a result, the hydride H^-Implanted into a Si wafer. Since the entire surface is in contact with the plasma, the hydride ions can be implanted into the entire surface at once. Since only one kind of negative ion is generated, mass separation is not required. Since the beam diameter is not reduced, no scanning mechanism is required.

[ fifth embodiment]

Fig. 7 shows a fifth embodiment. In this embodiment, a sputtering type negative ion source using cesium is employed. For example, the following documents disclose a sputtering type negative ion source using cesium.

(12) "chromatography for Extracting Oxygen and Fluorine neutral Ion from RFplasma spraying Type neutral Ion Source" Proc. BEAMs 1995, Tokyo, pp.191-194 of Tetsuo Tomioka, Hiroshi Tuji, Yoshitaka Toyoda, Yasuhito Goto and JunzoIshikawa et al.

The conductive target 101 is disposed at an upper portion of the plasma generation chamber 100. The axis of the target 101 may pass through the insulating member 102 to discharge electricity to the outside, and is connected to the negative bias power supply 103. The raw material gas is supplied through a gas inlet 104. A high-frequency coil 105 wound several turns is disposed in the plasma generation chamber 100. A tap of the high-frequency coil 105 may pass through the insulating member 106 to discharge to the outside. One end of the tap may pass through the matching box 107 and the first switch 108 to be connected to the high frequency power supply 109. One end of the high-frequency power supply 109 is grounded. The other end of the high-frequency coil 105 is in contact with the ground. The susceptor 110 and the wafer 111 are disposed at a lower portion of the plasma generation chamber 100. The shaft 112 may pass through the insulating member 113 so as to extend to the outside. The shaft 112, the susceptor 110, and the wafer 111 are connected to a second switch 114 and a forward bias power supply 115. The positive bias power supply 115 supplies the hydrogen ions with acceleration energy of 20KeV to 220 KeV. The timing adjustment circuit 116 turns on/off the first and second on/off switches 108 and 114 in the form of pulses at the timings shown in fig. 3A and 3B.

The oven 117 is disposed outside the plasma generation chamber 100. Cesium Cs118 is contained in oven 117. Heaters 119 disposed around the oven can heat the oven 117. The duct 120 is disposed on the oven 117. A nozzle 121 provided at the lead-out end of the pipe is disposed to face the lower surface of the target 101. When Cs is heated by the heater 119, steam is generated, which is ejected from the nozzle 121 so as to be able to adhere to the surface of the target 101. A gas outlet is formed downstream of the extraction electrode, allowing the internal pressure to be reduced to vacuum. The operation of the above structure will be described.

A negative voltage of about 300V-800V is applied to the target 101. Cesium vapor is generated from the oven 117 so that the vapor can adhere to the target 101. A mixed gas of a sputtering gas such as argon Ar, xenon Xe, or the like and hydrogen gas is introduced into the plasma generation chamber 100. A portion of the hydrogen molecules are adsorbed onto the cesium layer surface of the target. The first switch 108 is closed so that the high-frequency voltage is applied to the high-frequency coil 105. The high frequency vertically oscillates electrons in the gas so that they collide with atoms, thereby ionizing the electrons. Thus, plasma of the mixed gas (Xe + H) can be generated. The plasma is a collection of electrons, positive ions, neutral radicals, and neutral molecules.

Since a negative voltage is applied to the target 101, positive ions such as Xe in the inert gas in the mixed gas⁺The ions are attracted to the target. The positive ions of the inert gas collide with hydrogen molecules of the target to sputter the target. The hydrogen molecules take electrons off Cs and are decomposed, so that the hydrogen molecules are formed as monoatomic anions H^-. Since Cs is used, the density of negative ions can be increased. Although hydride ions can be generated, the scheme described in the first embodiment is employed. Immediately after the power supply to the high-frequency coil in the form of a pulse, the timing adjustment circuit 116 biases the wafer 111 to a positive voltage.

When a high frequency is applied to the high frequency coil 105, the high frequency strongly moves electrons to generate plasma. Upon interruption of the high frequency supply, the electrons lose kinetic energy. The probability of collision with neutral hydrogen molecules is thus increased. The main part of the low-velocity electrons attaches to neutral hydrogen, turning it into negative ions. In particular, by adjusting the amount of cesium which must be added, it is possible to produce a unipolar H^-. At this time, a positive bias is applied to the wafer, and negative ions can be efficiently implanted into the wafer.

There is a problem in the above method that Cs on the Si substrate or Cs implanted in a short distance must be removed. However, the advantage of high efficiency of generating negative ions can be obtained. During the discharge interruption (51 in fig. 3A and 3B), hydride ions are not implanted into the substrate (Si wafer). Since the plasma is always kept in a neutral state, the positive ions collide with the wall of the plasma generation chamber and the like. The positive ions collide with the target covered with cesium, thus further increasing the density of negative ions. Since electrons are supplied from the negative bias power supply 103, negative ions can be generated at high density.

Fig. 8 shows the process of the present invention in which hydride ions are less implanted into a Si substrate to form a porous film composed of hydrogen. Then, other Si ions may be attached to the porous film to separate Si, thereby manufacturing an SOI substrate. Briefly, (1) the surface of the first Si substrate is oxidized, thereby forming SiO₂And (3) a membrane. Then, (2) implanting hydride ions, thereby forming a porous layer having a high porosity. And (3) performing heat treatment to recover the damage of the surface Si layer caused by the implantation operation. Then, (4) bonding the first Si substrate. Then, (5) applying a shear force in the vertical direction, and cutting out the first substrate at the porous layer. And (6) polishing the surface. An SOI substrate can then be manufactured.

The negative hydrogen ions are implanted into a substrate made of a semiconductor, metal or insulating material so that hydrogen is buried at a predetermined depth. Since ions are implanted in a state where the entire substrate made of a semiconductor, a metal, or an insulating material is in contact with plasma. Ions can be implanted into the entire surface of the substrate in a concentrated manner. By adjusting plasma parameters, only hydride H can be generated in a unipolar form^-. When a positive plasma bias is periodically applied to the substrate, only H is present^-Stably injected in a required amount in a short time. The need to provide a mass separation system can be eliminated. Since a huge apparatus for mass separation is not required, the cost of the apparatus can be reduced. In addition, the area required for mounting the apparatus can be reduced. Since no mass separation is performed, the need to reduce the beam diameter can be eliminated. In addition, no scanning is required. Since the concentrated implantation can be performed without scanning, the yield can be improved.

In addition, the plasma generating device is periodically turned on/off to apply a forward biased plasma to the substrate when the plasma generating device is turned off. Overheating of the substrate due to over-irradiation of electrons and an increase in the capacity of the plasma bias power supply can be prevented. Therefore, a low-cost, stable ion implantation apparatus requiring a small mounting area can be provided.

Sixth embodiment (passing low-energy electrons through an energy filter)

There are many ways to generate hydride ions in large quantities. In particular, many results have been obtained in developing a source of hydride ions for a neutral particle implantation apparatus (NBI: neutral beam implantation) used in nuclear fusion research. The sixth embodiment adopts the above-described technique, and the following documents disclose the structure and operation of the hydride source.

The plasma chamber is divided by a magnetic field into a first plasma chamber and a second plasma chamber. When a current passes through the plurality of parallel conductive rods, a weak magnetic field of about several tens of gauss is formed. The above structure is referred to as an "energy filter". The energy filtering prevents a large number of energetic electrons of about several tens eV generated in the first plasma chamber from being introduced into the second plasma chamber.

In the second plasma chamber, a plasma is generated containing a plurality of low energy electrons in the range of about 1eV to about 0.1 eV. Electron-dissociably attaches to hydrogen molecules resulting in the production of large quantities of H^-。

A voltage having the polarity shown was applied to a porous electrode system disposed between the second plasma chamber and the Si substrate to extract a beam of hydride ions. The energy of about 10KeV-100KeV is applied to the hydride beam, so that the hydride beam is implanted to the required depth. At least one of the porous electrodes has a magnetic field shape device to extract mixed electrons and extract a negative ion beam by forming a weak magnetic field of about several tens gauss to several hundreds gauss in the beam extraction space.

Fig. 10 shows the sixth embodiment in detail. The energy filter adds low energy electrons and thus enhances the production of negative ions. Although the ECR plasma generating apparatus will be described below, the present invention may be applied to another excitation method. Plasma chamber 361 introduces gas inlet 362. The magnetron 364 generates microwaves 366. Microwaves 366 may pass through waveguide 365 and dielectric window 379 for introduction into plasma chamber 361. The coil 367 generates a magnetic field satisfying the ECR condition. That is, at a microwave of 2.45GHz, a magnetic flux density of 875 gauss can be achieved. The electron resonance then absorbs the microwave.

A plurality of parallel conductive bars 369 are disposed at a middle portion of the plasma chamber 361 to allow current to flow in the same direction. A magnetic field of about 10 gauss to about several tens of gauss is thus formed around the conductive rod 369. The magnetic field is formed in the housing direction, i.e., the magnetic flux density B is generated in the horizontal direction. The electrons make a helical motion around the horizontal magnetic field. Although the period of the helical motion is not energy dependent, its radius is proportional to the square of the energy. Since the faraday force is proportional to the electron velocity, it is amplified in the case of high-energy electrons. High-energy electrons cannot pass the potential barrier in the form of a weak magnetic field. Low energy electrons cannot pass through the potential barrier. Thus, the magnetic field generated by the conductive rods 369 acts as an energy filter, allowing low-energy electrons to selectively pass through.

The plasma chamber 361 is vertically divided into upper and lower portions by a conductive rod 369. The upper portion is a portion that resonantly absorbs microwaves and is referred to as first plasma chamber 368. The lower portion is a portion where negative ions are generated, and the lower portion is referred to as a second plasma chamber 370. The second plasma chamber 370 is open at a lower portion. The three extraction electrode systems are arranged below the opening. Acceleration electrodes 375, deceleration electrodes 376, and ground electrodes 377 are provided, each having a plurality of openings from which ion beams are extracted. The electrode is a porous electrode plate. In order to linearly extract the ion beam from the multi-aperture extraction electrode systems 375, 376 and 377, the ion beam transmission opening is formed at the same position. A susceptor 373 on which the Si wafer 372 is mounted is disposed in an upward position of the electrode. The base 373 is supported by a shaft 374. The voltage is a ground voltage (ground potential). The acceleration power supply 386(Vacc) has its positive terminal connected to ground and its negative terminal connected to the acceleration electrode 375 via a resistor 388. The negative electrode of the accelerating power supply 386 is also connected to the plasma chamber 361. The Vacc voltage is applied to the plasma chamber 361 and the accelerating electrode 375. A positive voltage is applied to the retardation electrode 376 through the retardation power supply 387. The potential of the ground electrode 377 is ground potential. The positive ions are confined in the plasma chamber 361 by an acceleration voltage Vacc. Only negative ions and electrons can pass through the acceleration electrode 375. The acceleration energy of the negative ions is q (Vpz + Vacc). This fact is a positive bias on plasma chamber 361 from the wafer perspective.

The positive bias Vacc is suitably determined based on the implantation depth of hydrogen into the Si wafer 372. For example, typical depths are achieved from about 10KeV to about 100 KeV. Negative ion beam H emitted by porous extraction electrode systems 375, 376, and 377^-Each having a large size, are implanted into a Si wafer 372. Since the distribution of the openings of each extraction electrode system is wide, the beam diameter is larger than the wafer diameter. Therefore, the negative hydrogen ions H can be injected at one time^-. No beam scanning mechanism is required. The reason that no scanning is required is that no mass separation is required. Since only one type of hydride is generated, no mass separation is required.

A plurality of permanent magnets 371 for confining plasma are disposed on an outer wall of a lower portion of the plasma chamber 61. The north and south poles are alternately reversed and placed between the adjacent magnets. Adjacent magnets generate cusp magnetic fields to confine charged particles to a middle portion of the plasma chamber. In this embodiment, the microwave excites the plasma. Alternatively, the plasma may be generated using a high frequency discharge or a DC discharge.

This operation will be described below. Hydrogen is introduced through gas inlet 362. Microwaves 66 are introduced into the plasma chamber 361 through the dielectric window 379. The electrons resonantly absorb the microwaves to generate a high density hydrogen plasma in the first plasma chamber 368. The plasma contains positive ions, electrons, neutral atoms, and molecules. Although containing only a small amount of negative ions, it contains a large amount of electrons. The electrons have a high energy of about 10eV,

a magnetic field B (several tens of gauss to 100 gauss) formed by the conductive rod 369 exists at the interface between the first plasma chamber 368 and the second plasma chamber 370. Charged particles are in particular potential barriers through which high-speed electrons cannot pass a magnetic field. Neutral atoms and molecules are capable of passing through a magnetic field B. Even light-weight electrons having low energy (about 1eV or less) can pass through the magnetic field B of the conductive bar 369. Although electrons of low energy are trapped by the magnetic field and thus undergo cyclotron motion, the electrons can be separated from the action of the magnetic field.

The second plasma chamber 370 does not satisfy the ECR condition. Therefore, the plasma is not increased. Only plasma moving from first plasma chamber 368 is present in second plasma chamber 370. That is, the plasma temperature is low. High-energy electrons are present in small amounts, while low-energy electrons are present in large amounts. The energy is about 1 eV. Low-energy electrons are dissociatively attached to neutral hydrogen molecules. Thus, hydride ions are generated. The major part of the low-energy electrons is attached to neutral atoms and molecules, which are then blanked. Therefore, the negative ion density is high. The negative ion beam is extracted from the second plasma chamber 370 by the acceleration electrode 375. The acceleration electrode 375 and the deceleration electrode 376 extract negative ions and electrons. The electrons are reduced and thus the proportion of negative ion beams is high. The electrons injected into the sample (wafer) do not have any benefit. There is a problem in that the substrate is undesirably heated. Therefore, it is preferable that the proportion of electrons is low. Thus, the energy filter is disposed at an intermediate height of the plasma chamber 361. It is effective to adopt a method of forming a weak magnetic field in the extraction electrode system to extract electrons.

In the sixth embodiment, hydrogen gas is supplied only to the first plasma chamber 368. The method is not limited thereto. Generally, when the hydrogen pressure is high, the efficiency of generating negative ions can be improved. To improve the efficiency of generating negative ions, hydrogen gas may be further supplied to the second separation chamber 370. The supply of hydrogen gas into the first plasma chamber may be prohibited and hydrogen gas may be supplied only to the second plasma chamber 370. In the above case, only the rare gas is introduced into the first plasma chamber. Some gas is required to generate the plasma.

As shown, the bias voltage is always applied to the accelerating 375 and decelerating 376 electrodes of the extraction electrode system. Alternatively, a switch may be provided between the accelerating electrode, resistor 388, and power supplies 386 and 387. These switches are repeatedly turned on/off to extract a negative ion beam from the plasma. Since it takes a long time to generate negative ions, the extraction is intermittently performed to supplement the negative ions, followed by extraction.

In this embodiment, the microwaves are continuously oscillated. Therefore, the temporary blanking of the plasma is no longer employed. Note that the post-cut negative ion beam method described above can be applied to this embodiment. Therefore, the magnetron may be intermittently oscillated to turn on/off the plasma according to the timing waveforms shown in fig. 3A and 3B. The reason for this is that the low-speed electrons increase during OFF for the same reason as in the first embodiment. When the voltage + Vpd is applied to the accelerating electrode in the timing shown in fig. 3A and 3B, the negative ion beam can be extracted as the density of the negative ions increases.

(seventh embodiment (Low-energy Electron-pass energy Filter))

Fig. 11 shows a seventh embodiment. This embodiment is constructed such that the energy filter is constructed of permanent magnets 381-384 instead of the conductive rods. In addition to the permanent magnet 371 for forming the cusp magnetic field, permanent magnets 381-384 facing the same direction are disposed at the middle height of the plasma chamber 361. A magnetic flux density B directed in one direction is formed between the permanent magnets 381 and 382, and between the permanent magnets 383 and 384 so that different poles face each other. A weak magnetic field of several tens to 100 gauss is required. The magnetic flux density B interrupts the high-speed electrons, i.e. acts as an energy filter. Thus, the same effects as those obtained by the current passing through the collector bar structure shown in fig. 11 can be obtained. The permanent magnet 371 disposed at the lower portion generates a cusp magnetic field. The extraction electrode system into which the acceleration electrode 375, the deceleration electrode 376 and the ground electrode 377 are introduced extracts negative ions. The above-described structure is similar to that of the sixth embodiment. Since the negative ions are implanted all at once on the surface. No mass separation and beam scanning is required.

[ eighth embodiment]

Fig. 12 shows an eighth embodiment. In this example, a sputtering type negative ion source using cesium was employed. For example, the following documents disclose a sputtering type negative ion source using cesium.

(12) Tetsuo Tomioka, Hiroshi Tuji, Yoshitaka Toyoda, "chromatography for Extracting Oxygen and Fluorine neutral Ion from RFPlasma Sputting Type neutral Ion Source", Proc. BEAMs 1995, Tokyo, pp.191-194, of Yasuto Goto and JunzoIshikawa et al.

The conductive target 401 is disposed at an upper portion of the plasma generation chamber 400. The axis of the target 401 may pass through an insulating member 402 to discharge outward and be connected to a negative bias power supply 403. Raw material gas (Xe + H)₂) Supplied through gas inlet 404. A high-frequency coil 405 wound several turns is disposed in the plasma generation chamber 400. A tap of the high-frequency coil 405 may pass through the insulating member 406 so as to be discharged to the outside. One end of the tap may pass through a matching box 407 for connection to a high frequency power supply 409. One end of the high frequency power supply 409 is grounded. The other end of the high-frequency coil 405 is in contact with the ground.

A wide opening is formed at the lower portion of the plasma generation chamber 400. An extraction electrode system composed of three porous plates, which are an acceleration electrode 413, a deceleration electrode 414, and a ground electrode 415, is connected to the front end position. Negative ions are then extracted from the plasma generation chamber to be accelerated. The susceptor 410 and the wafer 411 are disposed in a sealed space below the extraction electrode systems 413, 414 and 415 (the chamber is omitted fromillustration). Shaft 412 has ground potential. Plasma generation chamber 400 is biased at a high negative voltage with respect to accelerated power supply 412. The voltage level is determined according to the depth of the hydride ion implantation into the substrate, and the voltage level is about 20KeV to about 200 KeV. For example, a negative voltage of 100KV is applied to the plasma generation chamber. The cathode of the acceleration power source 422 is connected to the acceleration electrode 413 through a resistor 424. The same negative voltage as the acceleration power supply 422 is applied to the acceleration electrode 413. A positive voltage is applied to the retardation electrode 414 by the retardation power supply 423. The voltage of the accelerating electrode 413 is the same as that of the plasma generating chamber 400. Thus, the positive ion beam is inhibited from being discharged outward. Only the negative ions pass through the opening of the accelerating electrode 413 to be rapidly accelerated by the decelerating electrode 414.

The oven 417 is disposed outside the plasma generation chamber 400. Cesium Cs418 is contained in an oven 417. A heater 419 disposed around the oven can heat the oven 417. The duct 420 is disposed on the oven 417. A nozzle 421 provided at the outlet end of the duct is provided to face the lower surface of the target 401. When Cs is heated by the heater 419, steam is generated, and the steam is ejected from the nozzle 421 so as to be allowed to adhere to the surface of the target 401. A gas outlet 422 is provided to the plasma generation chamber 400 so that the internal pressure can be reduced to vacuum. The operation of the above-described structure will be described below.

A negative voltage of about 300V-800V is applied to the target 401. Cesium vapor is generated from the oven 417 so that the vapor can adhere to the target 401. A mixed gas of a sputtering gas such as argon Ar, xenon Xe,or the like and hydrogen gas is introduced into the plasma generation chamber 400. A portion of the hydrogen molecules are adsorbed onto the cesium layer surface of the target.

A high-frequency voltage is applied to the high-frequency coil 405. The high frequency vertically oscillates electrons in the gas so that they collide with atoms, thereby ionizing the electrons. Thus, plasma of the mixed gas (Xe + H) can be generated. The plasma is a collection of electrons, positive ions, neutral radicals, and neutral molecules.

Since a negative voltage is applied to the target 401, positive ions of the inert gas such as Xe in the mixed gas⁺The ions are attracted to the target and the positive ions of the inert gas collide with the hydrogen molecules of the target to sputter the target. The hydrogen molecule takes out electrons from Cs and is decomposed, so that the hydrogen molecule is formed into a monoatomic anion H^-. Since Cs is used, the density of hydrogen ions can be increased. H^-An ion beam is extracted from the high density hydride containing plasma for irradiating the wafer 411. Thus H^-May be implanted to a predetermined depth in the wafer.

The above method has a problem that Cs on the Si substrate or Cs implanted into a short distance must be removed. However, an advantage of efficiency in generating negative ions can be obtained. As the negative hydrogen ions are implanted into the wafer, the density of negative ions in the plasma may decrease. Since the plasma always maintains a neutral state, positive ions collide with the target covered with cesium, take out electrons from Cs, and supply the electrons to neutral hydrogen. Thus, the negative ions H are regenerated in an amount corresponding to the blanked negative ions^-。

By adopting a method of a structure that is switched on/off in a pulsed manner instead of the high-frequency coil, high-density hydride ions can be generated. That is, the negative hydrogen ions can be continuously injected. The Cs sputtering negative ion source was intermittently operated in a pulse manner similar to the sixth and seventh embodiments. Although the three extraction electrode system is employed in the first, second, and third embodiments, a double extraction electrode system incorporating an accelerating electrode and a ground electrode may be employed.

(ninth embodiment (post-cut negative ion beam method))

Referring to fig. 13, a ninth embodiment will be described. Microwaves are introduced into the target chamber through the antenna to generate plasma in the chamber. Coaxial cable 331 is connected to MP cathode chamber 328 having raw material gas inlet 329. The antenna 332 is fixed to the outlet of the coaxial cable 331. The microwaves generated in the magnetron (not shown) are transmitted in a coaxial cable to be introduced into the MP cathode chamber 328 through the antenna 332. Hydrogen is introduced into chamber 328.

The magnetic field applying unit 333 generates a vertical magnetic field in the MP cathode chamber 328. Thus, a microwave resonance magnetic field is generated. The electrons emitted from the hydrogen gas resonate and absorb the microwaves. The movement of electrons is enhanced to attach hydrogen. Thus, a hydrogen plasma is generated, which contains positive ion hydrogen and electrons. A rare gas, such as Ar or He, may be added. If no addition is made, only positive ions are generated, and therefore the object cannot be achieved.

Thus, main discharge chamber 330 abuts MP cathode chamber 328. The main discharge chamber 330 has no plasma excitation source of its own. The main discharge chamber 330 is filled with hydrogen plasma drifting from the MP cathode chamber 328. A plurality of permanent magnets 335 having different polarities, e.g., NS, SN …, are coupled to the outer wall of the main discharge chamber 330. A cusp magnetic field is then generated in the chamber to prevent charged particles in the plasma from colliding with the walls. The magnetic field is a cusp magnetic field for confining the plasma. An arc power supply 339(Vex) is disposed between the main discharge chamber 330 and the MP cathode chamber 328. The main discharge cells 330 are biased with a positive voltage of Vex. As a result, electrons and negative ions are introduced from the MP cathode into the main discharge chamber 330 through the electron discharge port 334. The electrons release energy for generating a main discharge plasma 357. In addition to the electrons, hydrogen positive and negative ions move to the main discharge chamber 330. Electrons fly in this space, striking hydrogen, thereby generating positive and negative ions. At high energies, electrons are repelled, generally creating positive ions. At low energy, hydrogen electron orbitals are introduced, and thus negative ions are generally generated. The function of the electrons has the above-mentioned two-sidedness.

When positive ions are generated, electrons increase, and when negative ions are generated, electrons decrease. Electrons are continuously supplied from the MP cathode. Electrons collide with hydrogen atoms and molecules, and the electrons lose energy. The low-speed electrons adhere to hydrogen atoms and sometimes generate negative ions. However, a major portion of the low-speed electrons collide with the wall of the main discharge cell, and thus, the major portion is extinguished.

The main discharge plasma 357 contains hydrogen positive ions, electrons, hydrogen negative ions, neutral hydrogen molecules, and neutral atoms. Opposite sides of the main discharge cells 330 are formed as openings. An extraction electrode system consisting of three perforated plates, acceleration electrode 336, deceleration electrode 337 and earth electrode 338, is provided at the front end of the opening. When three porous electrodes are collectively referred to, they are referred to as "extraction electrode systems". When these electrodes must be referred to individually, they are referred to as acceleration electrodes, deceleration electrodes, and ground electrodes. The structure is not limited to the three-electrode system, and a two-electrode system may be employed. In the above case, the acceleration electrode and the ground electrode are provided, and the deceleration electrode is omitted. In the following examples, a three lead electrode system will be described. The above extraction electrode system extracts negative ions as a beam from the main discharge chamber 330. The acceleration power source 342 is connected to the acceleration electrode 336 through the second switch 344 and the resistor 341. The main discharge chamber 330 is biased to a high negative voltage when the second switch 344 is turned off. That is, the magnitude thereof is the difference between the acceleration voltage Vacc and the extraction voltage Vex (Vacc-Vex). The voltage of the acceleration electrode 336 is-Vacc. The deceleration electrode 337 is connected to a deceleration power source 343 through a third switch 345 so as to apply a positive voltage.

When the second switch 344 and the third switch 345 are closed, negative ions are extracted from the main discharge chamber 357 by Vacc. When the first switch 340 is turned off, electrons and negative ions are introduced from the MP cathode into the main discharge chamber 30. Thus, a main discharge plasma 357 containing a large amount of negative ions is generated. Naturally, all the switches 340, 344 and 345 may be turned off to continuously extract negative ions, so that hydrogen negative ions are implanted into the Si wafer 358 by the timing adjusting circuit 347. With the positive bias applied by the retardation electrode 337, only negative ions and electrons are injected into the Si wafer 358. The injection of electrons that are not impurities does not cause serious problems. Naturally, the negative ions can be implanted continuously.

If electrons and negative ions are injected at the same time, a large amount of electric power corresponding to the electron current is wasted. In addition, heating caused by electron impact cannot be ignored. Therefore, the proportion of negative ions needs to be increased. To increase this ratio, a method of increasing and decreasing the negative ion density after plasma cutting is employed. To take advantage of the above fact, each switch is turned on/off in a pulsed manner, as shown in fig. 3A and 3B. Fig. 3A shows the timing of the opening/closing of the first switch 340, with a repeating waveform consisting of OFF 51, first transition 48, ON 49, falling edge 50, and OFF 51. Fig. 3B shows the timing of the opening/closing of the second switch 344 and the third switch 345, the repeating waveform consisting of OFF 56, first transition 53, ON 54, and falling edge 55. Note that there is some degree of delay in performing the latter operation. The OFF (52) state is maintained when the first switch 340 is on the falling edge 50. After a certain delay, a first switching (53) of the second and third switches is performed. The delayed ON/OFF operation described above is repeated indefinitely.

The delay circuit 346 controls the switching operation of the three switches 340, 344, and 345. When the first switch is off, main discharge plasma 357 is formed (ON 49). When the first switch 340 is opened, the temperature of the plasma is rapidly decreased, and thus the electrons lose their energy. Although the electrons in the plasma have an energy of about 10eV at the beginning, the energy decreases to about 1eV to 0.1eV a few microseconds after the first switch 340 is opened. That is, the electrons become low-speed electrons. The low-velocity electrons have a large cross-sectional area for collision and attachment. The low-speed electrons collide with the neutral hydrogen atoms, and can adhere to the neutral hydrogen atoms, turning the hydrogen atoms into negative ions. Thus, the density of negative ions rises to a level equal to that of positive ions. At this time 352, the second and third switches 344 and 345 are closed. As a result, the

extraction electrode systems

336, 337, and 338 extract the negative ion beam. Because of the high density of negative ions, only negative ions are efficiently extracted. The extraction voltage is cut off (55) because negative ions are consumed. The most preferred delay time τ from the falling edge 50 of the first switch to the first transition 53 of the second switch is about 10 microseconds. Since the pulse operation is repeatedly performed. The interval (delay time) τ between 50 and 53 must be 10 microseconds until off.

As a result, the electrode is only biased negative when the main discharge plasma has a high density of hydrogen negative ions. Thus, a negative ion beam can be extracted and implanted into the wafer. Although the electron current is ineffective, the electron current is reduced and a large amount of negative ion beams are extracted when the on/off is performed at the above timing. In this embodiment, switches 340, 344, and 345 are semiconductor switches. In the above case, it was confirmed that a duty ratio of 1% was allowed, and a repetition frequency of several Hz to 10KHz was allowed. Thyristors may be used as switching means.

The essential part of the ninth embodiment is to switch on/off the plasma to generate H in large quantities during the plasma off period^-. With a proper timing, a predetermined bias voltage is applied to the extraction electrode system so that H^-Implanted into a Si substrate. Therefore, the phenomenon that negative ions are increased immediately after the plasma is cut off is skillfully utilized.

Although a high frequency excitation device is employed, the device is not limited thereto. As for the plasma generating device, microwave plasma or DC discharge plasma may be employed instead of the high-frequency plasma. In any case, the plasma generating device is periodically turned on/off, and a predetermined bias voltage is applied to the extraction electrode system at a timing at which negative ions are increased immediately after the plasma generating device is turned off. The opposite fact will be described below. In the ninth embodiment, the generation (first switch 340) and extraction (second and third switches) of plasma are performed in a pulsed manner to extract the ion beam only when the hydride density is high. The above method can be used in the following examples. Although a specific description is omitted, the continuous plasma generation and beam extraction shown in fig. 3 can be used in any of the above embodiments.

Hydride ions are implanted into a semiconductor substrate, a dielectric substrate, or a metal substrate so that a large number of hydrogen-containing layers can be formed at a predetermined depth. Hydrogen is extracted from the plasma as a negative ion beam by an extraction electrode system. Since the diameter of the ion beam is larger than that of the substrate, the hydride H can be concentrated^-Implanted into the surface of the substrate. Only the hydride is stable to produce a single polarity. At a predetermined plasmaWhen the sub-bias is periodically applied to the extraction electrode system, only H^-Stably injected in a required amount in a short time. No mass separation system is required. Thus, a large-sized apparatus for mass separation is not required. Therefore, the equipment cost can be reduced. In addition, the area required for mounting the apparatus can be reduced. Since no mass separation is performed, the need to reduce the beam diameter can be eliminated, eliminating the need for scanning. Since the scan is not performed, the injection can be concentrated, so that the yield can be improved.

In addition, the plasma generating device is periodically turned on/off, and then a voltage is applied to the extraction electrode system. Thus, negative ions can be efficiently extracted. Thus, it is possible to prevent overheating of the substrate caused by excessive electron radiation and an increase in the power supply capacity for extracting the electronic system. Therefore, a low-cost and stable ion implantation apparatus requiring a small mounting area can be provided.

Claims

1. A method of implanting hydride ions, comprising the steps of:

generating a hydrogen-containing plasma;

generating hydride ions in the plasma;

forming an electric field between the plasma and the substrate; and

the negative hydrogen ions from the plasma are accelerated by the electric field to implant the negative hydrogen ions to a predetermined depth of the substrate.

2. The method of implanting hydrogen anions according to claim 1, characterized in that one or more substrates are provided, and hydrogen anions are implanted into the entire surface of the one or more substrates without mass separation from the plasma.

3. The method of implanting hydrogen anions according to claim 1, wherein the substrate is heated to form the cavity at a predetermined depth during or after the implanting of the hydrogen anions.

4. The method of implanting hydrogen anions according to claim 1, wherein the hydrogen anions are accelerated by providing a plurality of extraction electrodes between the plasma and the substrate, and applying a voltage to the plurality of extraction electrodes to form an electric field between the extraction electrodes, thereby extracting the hydrogen anions from the electric field.

5. Method for implanting hydride ions according to claim 4, characterized in that the plasma is periodically switched on/off.

6. A method for implanting hydrogen negative ions according to claim 1, wherein the substrate is exposed to plasma, the plasma is periodically turned on/off, and a positive plasma voltage is applied to the substrate within a period of about 10 μ s from when said plasma is turned off to when said plasma is turned on, so that the negative ion beam in the plasma in a extinguished state is accelerated and thereby implanted into the substrate.

7. An apparatus for implanting negative hydrogen ions, comprising:

a hydrogen generating device for generating plasma-containing hydrogen;

a negative hydrogen ion generator for generating negative hydrogen ions in the plasma; and

electric field forming means for forming an electric field between the plasma and the substrate;

wherein the negative hydrogen ions from the plasma are accelerated by the electric field to implant the negative hydrogen ions to a predetermined depth of the substrate.

8. The apparatus for implanting hydrogen anions according to claim 7, characterized in that the one or more substrates are provided and hydrogen anions are implanted into the entire surface of the one or more substrates without mass separation from the plasma.

9. The apparatus for implanting hydrogen anions according to claim 7, further comprising heating means for heating the substrate to form the cavity at a predetermined depth during or after the implanting of hydrogen anions.

10. The apparatus for injecting hydrogen anions according to claim 7, further comprising a plurality of extraction electrodes between the plasma and the substrate for accelerating the hydrogen anions;

wherein a voltage is applied to the plurality of extraction electrodes to form an electric field between the extraction electrodes, thereby extracting hydride ions from the electric field.

11. The apparatus for injecting hydrogen anions according to claim 10, characterized in that the plasma generating device is periodically turned on/off.

12. The apparatus for implanting hydrogen negative ions according to claim 7, wherein the substrate is exposed to plasma, the plasma device is periodically turned on/off, and a positive plasma voltage is applied to the substrate within a period of about 10 μ s from when said plasma is turned off to when said plasma is turned on, so that the negative ion beam in the plasma in a extinguished state is accelerated and thereby implanted into the substrate.

13. A method of implanting pulsed bias hydrogen anions to a predetermined depth in a substrate, comprising the steps of:

generating hydrogen-containing plasma by using a plasma generating device;

exposing the substrate to a hydrogen plasma;

a positive plasma voltage is applied to the substrate to implant hydrogen negative ions contained in the plasma to a predetermined depth of the substrate.

14. A method for injecting pulsed bias hydrogen anions as claimed in claim 13 wherein the magnetic field for trapping electrons is formed in the middle portion of a plasma chamber for generating plasma, the plasma generating means generates plasma in a first plasma chamber located on either side of the magnetic field, the substrate is disposed in a second plasma chamber where the magnetic field inhibits movement of energetic electrons to said second plasma chamber where collisions of electrons, neutral atoms and molecules are enhanced so that the concentration of hydrogen anions is increased.

15. A method for injecting pulsed negative hydrogen ions according to claim 1, wherein Cs is supplied to a plasma chamber introducing means for generating plasma by applying a high frequency to a high frequency coil, Cs being placed on a surface of a conductive target provided in said plasma chamber, and a negative voltage being applied to said target to sputter said target with positive ions, thereby generating hydrogen plasma containing negative hydrogen ions at a high concentration.

16. A method for implanting pulsed negative hydrogen ions according to claim 1, wherein said plasma generating means is periodically turned on/off, and a positive pulse voltage is applied to the substrate during a period from when said plasma generating means is turned off to when said plasma generating means is turned on again after 10 μ s.

17. An apparatus for implanting pulsed bias hydride ions, comprising:

a plasma chamber, which is a space where plasma is generated, and which can be changed into a vacuum state;

plasma generating means for generating a plasma in said plasma chamber;

a gas introduction opening for introducing a hydrogen atom-containing gas into said plasma chamber;

a gas exhaust unit for exhausting gas from the plasma chamber;

a susceptor disposed in said plasma chamber, on which a substrate is disposed;

a forward bias power supply for applying a forward bias voltage to said base;

a switch disposed between said forward bias power supply and said base; and

a mechanism for applying a positive bias to the substrate in a pulsed manner.

18. An apparatus for injecting pulsed bias hydrogen anions as claimed in claim 5 further comprising magnetic field forming means for forming a magnetic field in said plasma chamber disposed in or on the exterior of said plasma chamber to divide said plasma chamber into two parts to prevent high energy electrons from passing therethrough by the magnetic field; wherein one of said plasma chambers generates a plasma and said susceptor and substrate are disposed in the other plasma chamber.

19. The apparatus for injecting pulsed bias hydrogen anions as claimed in claim 17, further comprising a conductive target disposed in said plasma chamber into which means for generating plasma by applying high frequency to a high frequency coil is introduced, a negative bias power source for applying negative pressure to said target, an oven for generating Cs, Rb or K vapor, and a nozzle for introducing the vapor generated from the oven into said target.

20. An apparatus for implanting pulsed negative hydrogen ions according to claim 5, further comprising means for turning on/off said plasma generating means, and further comprising a timing adjusting circuit for determining a timing for enabling/disabling plasma generation and enabling/disabling positive bias on said susceptor;

wherein a positive bias is applied to said pedestal immediately after said plasma generating device is turned off.

21. A hydride ion beam implanting method for implanting hydrogen ions to a predetermined depth of a substrate, comprising the steps of:

generating hydrogen-containing plasma by using a plasma generating device;

extracting a bundle of hydride ions from the plasma using an extraction electrode system incorporating a plurality of porous electrode plates each having pores distributed over a wider diameter than the substrate; and

the beam of hydride ions is implanted to a predetermined depth of the substrate.

22. A hydride ion beam implantation method according to claim 21, wherein a magnetic field for trapping electrons is formed in a central portion of a plasma chamber for generating plasma, the plasma is generated by a plasma generating device provided in a first plasma chamber on either side of the magnetic field, an extraction electrode system is provided in an opening portion of a second plasma chamber so as to prevent movement of high-energy electrons in the first plasma chamber by the magnetic field, collisions of low-energy electrons, neutral atoms and molecules in said second plasma chamber are intensified to provide a density of negative ions, so that a hydride ion beam is extracted from said second plasma chamber to inject the hydride ion beam into a substrate.

23. A method for implanting a hydrogen negative ion beam according to claim 1, characterized in that Cs is supplied to a plasma chamber into which a means for generating plasma by applying high frequency to a high frequency coil is introduced, Cs is deposited on the surface of a conductive target provided in said plasma chamber, and a negative voltage is applied to the target to sputter the target with positive ions, thereby generating hydrogen plasma containing a high concentration of hydrogen negative ions.

24. A method for implanting hydride ions as defined in claim 1, wherein said plasma generating means is periodically turned on/off, and a DC voltage is applied to said extraction electrode system for extracting the hydride ion beam from a period from when said plasma generating means is turned off to when said plasma generating means is turned on again for 10 μ s.

25. A hydride ion beam implantation apparatus comprising:

a plasma chamber, which is a space where plasma is generated, in which pressure can be reduced to vacuum;

plasma generating means for generating a plasma in said plasma chamber;

a gas exhaust unit for exhausting gas from the plasma chamber;

a plurality of extraction electrode systems disposed at an opening portion of the plasma chamber, each of which introduces a porous plate having a diameter larger than that of the substrate;

a power supply for applying a high negative voltage and a positive voltage to the extraction electrode system to extract a negative ion beam from the plasma; and

and a base disposed downstream of said extraction electrode system, on which a semiconductor substrate, an insulating substrate or a metal substrate is to be disposed.

26. A hydride ion beam implantation apparatus according to claim 25, further comprising magnetic field forming means for forming a magnetic field in said plasma chamber, provided in said plasma chamber or on an outside of said plasma chamber, to divide said plasma chamber into two parts, thereby preventing passage of energetic electrons by said magnetic field; wherein any one of said plasma chambers generates a plasma and said susceptor and substrate are disposed in another plasma chamber.

27. The hydride ion beam implantation apparatus as set forth in claim 25, further comprising a conductive target disposed in said plasma chamber into which a means for generating plasma by applying high frequency to a high frequency coil is introduced, a negative bias power source for applying a negative voltage to said target, an oven for generating Cs, Rb or K vapor, and a nozzle for introducing the vapor generated from the oven into said target.

28. The hydride beam implantation apparatus according to claim 5, further comprising:

a switch for turning on/off the plasma generating means;

a switch for switching on/off the plasma generation and the DC voltage applied to said extraction electrode system;

a delay circuit for determining a relationship between a timing of turning on/off the plasma generating means and a timing of turning on/off a voltage of the extraction electrode system;

wherein a DC voltage is applied to said extraction electrode system immediately after said plasma generating means is switched off to extract a negative ion beam.