CN101499620B - Nitride semiconductor device and method of manufacturing same - Google Patents
Nitride semiconductor device and method of manufacturing same Download PDFInfo
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- CN101499620B CN101499620B CN2009100079900A CN200910007990A CN101499620B CN 101499620 B CN101499620 B CN 101499620B CN 2009100079900 A CN2009100079900 A CN 2009100079900A CN 200910007990 A CN200910007990 A CN 200910007990A CN 101499620 B CN101499620 B CN 101499620B
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Abstract
Provided are a nitride semiconductor light emitting device including a coat film formed at a light emitting portion and including an aluminum nitride crystal or an aluminum oxynitride crystal, and a method of manufacturing the nitride semiconductor light emitting device. Also provided is a nitride semiconductor transistor device including a nitride semiconductor layer and a gate insulating film which is in contact with the nitride semiconductor layer and includes an aluminium nitride crystal or an aluminum oxynitride crystal.
Description
The application of this division is the Chinese patent application that is entitled as " nitride compound semiconductor device and preparation method thereof " number 200710085676.5 divides an application that proposes on March 6th, 2007.
This non-provisional application was based on March 6th, 2006 and be filed in the Japanese patent application No. 2006-059695 and the 2007-009282 of Japan Patent office on January 18th, 2007, and its full content is combined in this by reference.
Technical field
The present invention relates to nitride semiconductor photogenerator, prepare the method and the nitride semiconductor crystal tube device of nitride semiconductor photogenerator.
Background technology
Usually, in nitride semiconductor photogenerator, known nitride semi-conductor laser causes low reliability because of the degeneration of luminous component.It is believed that the existence owing to the non-radiation type combination level, the heat that excessively produces from luminous component causes the degeneration of luminous component.The oxidation of luminous component is considered to the main cause of non-radiation type combination level.
Therefore, in order to prevent the oxidation of luminous component, form alundum (Al (Al at luminous component
2O
3), silica (SiO
2) film (referring to, Japanese patent application publication No. 2002-335053 for example) that wait.
Summary of the invention
The present inventor studies, even be intended to realize when high power drives, does not also demonstrate the nitride semi-conductor laser of the low reliability that the degeneration because of luminous component causes.
For conventional nitride semi-conductor laser, each all has described laser the thick alundum (Al of 80nm that forms at the facet of emission side and films, and multilayer film with the silicon oxide film/oxidation titanium film that forms at the facet place of light reflection side, wherein reflectivity is 95%, the present inventor has carried out two kinds of ageing tests: (30 ℃ of low temperature and lower powered conditions, CW drives, luminous power 30mW) under ageing test; With the ageing test under high temperature and high-power condition (70 ℃, CW drives, luminous power 100mW).As a result, in the ageing test under low temperature and lower powered condition, described device steady operation was above 3000 hours.In the ageing test under high temperature and high-power condition, observe because at the COD of luminous component (catastrophe optical damage), many nitride semi-conductor lasers stopped luminous after about 400 hours.Therefore, in the nitride semi-conductor laser of routine, the COD that finds luminous component is the problem of 400 hours relative ageing times of lacking under high temperature and high-power condition.
Equally, driving under high temperature and the high-power condition under the situation of nitride semiconductor LED device, its light-emitting area, promptly luminous component may be degenerated, thereby causes the reliability of deterioration.In the nitride semiconductor crystal tube device such as HFET (hetero-structure field effect transistor) that use nitride-based semiconductor, also need the reliability that improves.
Therefore, an object of the present invention is to provide: even under high temperature and high power, be driven, the nitride semiconductor photogenerator that also has enough reliabilities, with the method for the described nitride semiconductor photogenerator of preparation, and the nitride semiconductor crystal tube device with reliability of raising.
The invention provides a kind of nitride semiconductor photogenerator of filming that luminous component forms that is included in.Described filming comprises aluminum nitride crystal or aluminium oxynitride crystal.
Preferably, in nitride semiconductor photogenerator of the present invention, aluminum nitride crystal or aluminium oxynitride crystal have the crystallographic axis of align with the crystallographic axis of the nitride semiconductor crystal that forms luminous component (aligned with).
Preferably, in nitride semiconductor photogenerator of the present invention, the thickness of filming is 6nm and 150nm at least at the most.
Preferably, in nitride semiconductor photogenerator of the present invention, on filming, form the film of making by oxide, oxynitride or nitride.
Preferably, in nitride semiconductor photogenerator of the present invention, the film of being made by oxide on filming is pellumina, silicon oxide film, oxidation titanium film, hafnium oxide film, zirconium oxide film, niobium oxide film, tantalum-oxide film or yittrium oxide film.
Preferably, in nitride semiconductor photogenerator of the present invention, the film of being made by oxynitride on filming is to have and different the aluminium oxynitride film or the oxygen silicon nitride membrane formed formed of filming.
Preferably, in nitride semiconductor photogenerator of the present invention, the film of being made by nitride on filming is aluminium nitride film or silicon nitride film.
Preferably, in nitride semiconductor photogenerator of the present invention, on filming, form the magnesium fluoride film.
Nitride semiconductor photogenerator of the present invention is a nitride semi-conductor laser, and can form described filming on the facet of the emission side of nitride semi-conductor laser.
Nitride semiconductor photogenerator of the present invention is the nitride semiconductor LED device, and can form described filming on the light-emitting area of nitride semiconductor diode device.
At this, be under the situation of nitride semi-conductor laser or nitride semiconductor LED device at nitride semiconductor photogenerator of the present invention, preferably use by forming structural formula Al
sGa
tThe substrate that the nitride system semiconductor of N (s+t=1,0≤s≤1,0≤t≤1) expression becomes is as substrate.At this, in above-mentioned composition structural formula, Al represents aluminium, and Ga represents gallium, and N represents nitrogen, and s represents the composition ratio of aluminium, and t represents the composition ratio of gallium.
The present invention also provides a kind of method for preparing aforesaid nitride semiconductor photogenerator.Described method comprises the steps: to use argon or nitrogen plasma irradiation luminous component; And after the irradiation of plasma, form aluminum nitride crystal or aluminium oxynitride crystal at luminous component.
Preferably, in the method for preparation according to nitride semiconductor photogenerator of the present invention, the formation temperature of the formation temperature of aluminum nitride crystal or aluminium oxynitride crystal is 200 ℃ at least.
In the method for preparation, can use by Al according to nitride semiconductor photogenerator of the present invention
xO
yThe target that the composition structural formula of (0＜x＜1,0＜y＜0.6) is represented forms the aluminium oxynitride crystal with aluminium oxide, and wherein Al represents aluminium, and O represents oxygen, and x represents the composition ratio of aluminium, and y represents the composition ratio of oxygen.
The present invention provides a kind of nitride semiconductor crystal tube device in addition, and described device comprises nitride semiconductor layer and the gate insulating film that contacts with described nitride semiconductor layer.Described gate insulating film comprises aluminum nitride crystal or aluminium oxynitride crystal.
Preferably, in nitride semiconductor crystal tube device of the present invention, aluminum nitride crystal or aluminium oxynitride crystal have the crystallographic axis that aligns with the nitride semiconductor crystal that forms nitride semiconductor layer.
According to the present invention, even a kind of nitride semiconductor photogenerator that also has enough reliability when being driven under high temperature and high power can be provided; With a kind of method for preparing described nitride semiconductor photogenerator; And a kind of nitride semiconductor crystal tube device with reliability of raising.
From the following detailed description of the present invention in conjunction with the accompanying drawings the time, it is more obvious that above and other objects of the present invention, feature, aspect and advantage will become.
Description of drawings
Fig. 1 is the cross-sectional view that is schematically illustrated in a preferred embodiment of a nitride semi-conductor laser in the embodiment.
Fig. 2 is the end view of nitride semi-conductor laser on the cavity length direction that schematically shows in the embodiment shown in Figure 1.
Fig. 3 has schematically shown a kind of structure of exemplary ECR sputter deposition apparatus.
Fig. 4 is near the TEM photo of facet of the emission side of nitride semi-conductor laser in the first embodiment.
Fig. 5 has shown the image K-M at the TEM of the regional A shown in Fig. 4.
Fig. 6 has shown the image K-M at the TEM of the area B shown in Fig. 4.
Fig. 7 has shown the nitride semi-conductor laser in the first embodiment, the measurement result of the COD level before aging and after aging.
Fig. 8 has shown the relation between the COD of the nitride semi-conductor laser of routine level and ageing time.
Fig. 9 is the cross-sectional view that schematically shows according to a preferred embodiment of nitride semiconductor crystal tube device of the present invention.
Figure 10 is the cross-sectional view that schematically illustrates at an example of the stripping film at the facet place of nitride semi-conductor laser.
Embodiment
Below, embodiment of the present invention will be described.Attention is in accompanying drawing of the present invention, and identical reference symbol is represented identical or corresponding part.
In order to address the above problem, the inventor has studied (30 ℃ of low temperature and lower powered conditions, CW drives, luminous power 30mW) after down aging and (70 ℃ of high temperature and high-power conditions, CW drives, luminous power 100mW) after down aging, has the COD level that the conventional nitride semi-conductor laser of above-mentioned structure changes separately.
Fig. 8 has shown the relation between the COD of conventional nitride semi-conductor laser level and ageing time.In Fig. 8, axis of abscissas is represented ageing time, and axis of ordinates is represented the COD level.At this, the COD level refers to in the nitride semi-conductor laser that has behind the ageing time that changes under condition as mentioned above aging each, when by increasing drive current (CW driving) gradually when increasing luminous power, the optical power value that obtains when luminous component suffers COD.
As shown in Figure 8, after wearing out under low temperature and lower powered condition, nitride semi-conductor laser is owing to the COD of luminous component degenerates in about 50 hours ageing time.Yet even after longer ageing time, the COD level also changes hardly.
On the other hand, after wearing out under high temperature and high-power condition, nitride semi-conductor laser is owing to the COD of luminous component degenerates in about 50 hours ageing time.Before about 200 hours ageing time, the COD level does not descend significantly.Yet, after 400 hours ageing time, observe the decline significantly of COD level.
Based on The above results, the inventor finds, in the ageing process under high temperature and high-power condition, owing to the decline of COD level after 400 hours ageing time, causes the reliability deterioration of nitride semi-conductor laser.
The inventor thinks: aerial oxygen or O-H group are by the alundum (Al that forms at the facet of the emission side transmission of filming, arrival is formed on the surface of the faceted nitride semiconductor crystal of emission side, thereby the nitrogen oxide semiconductor crystal causes the deterioration of COD level.In other words, it is believed that filming to transmit by the thick alundum (Al of 80nm needs about 400 hours for airborne oxygen or O-H group.
In most of the cases, by EB (electron beam) deposition, sputter or any other method, be grown in filming that the facet of emission side forms.In this case, known filming almost is amorphous.After carrying out above-mentioned test, the facet of nitride semi-conductor laser is carried out TEM (transmission electron microscope) observe, the image K-M of filming with observation.At this, observe noncrystal distinctive ring of light image, be amorphous thereby confirm to film.
Have low-density and comprise many defectives because amorphous is filmed, so the inventor thinks that aerial oxygen or O-H group can easily film by amorphous.So as the result who studies in great detail, the inventor finds, comprises filming of aluminum nitride crystal or aluminium oxynitride crystal by the luminous component formation at nitride semiconductor photogenerator, can obtain the enough reliabilities under high temperature and high power driving.Thereby finished the present invention.
In addition, as the result who studies in great detail, the inventor finds, when the crystallographic axis of aluminum nitride crystal in filming or aluminium oxynitride crystal aligns with the crystallographic axis of the nitride semiconductor crystal that forms luminous component, can further improve the reliability under high temperature and high power driving.
Preferably in the present invention, the thickness of filming is 6nm and 150nm at least at the most.If it is so to approach the transmission by filming such as consequently can not fully suppressing oxygen that the thickness of filming less than 6nm, is then filmed.On the other hand, if the thickness of filming surpasses 150nm, then because filming of crystallization has than the amorphous stronger internal stress of filming, it may be crannied filming.
In the present invention, if make by the aluminium oxynitride crystal film in oxygen content be higher than the 35 atom % that constitute all atoms of filming, it is approaching with the character of alundum (Al then to film, and the crystallinity of aluminium oxynitride crystal may be lost.Thereby can not fully suppress the transmission by filming such as oxygen.Therefore, in the present invention, make by the aluminium oxynitride crystal film in oxygen content be preferably and be equal to or less than 35 atom %, and more preferably be equal to or less than 15 atom %.
At this, nitride semiconductor photogenerator of the present invention for example comprises, nitride semi-conductor laser or nitride semiconductor LED device.In addition, nitride semiconductor photogenerator of the present invention refers to be included in the active layer that forms on the substrate and the luminescent device of coating, described substrate is to be formed by the material that comprises the compound that is equal to or greater than 50 quality %, and described compound is by being selected from the 3rd at least a family's element in aluminium, indium and the gallium and forming as the nitrogen of the 5th family's element.
In addition, nitride semiconductor crystal tube device of the present invention for example comprises, uses the HFET of nitride-based semiconductor.
(first embodiment)
Fig. 1 is the cross-sectional view that is schematically illustrated in a preferred embodiment of the nitride semi-conductor laser in the present embodiment.At this, the nitride semi-conductor laser in the present embodiment 100 is configured to comprise: the thickness of being made by n type GaN is the resilient coating 102 of 0.2 μ m, by n type Al
0.06Ga
0.94The thickness that N makes is the n type covering 103 of 2.3 μ m, and the thickness of being made by n type GaN is the n type guide layer covering 104 of 0.02 μ m, and the Multiple Quantum Well active layer of being made by thick InGaN of 4nm and the thick GaN of 8nm 105 is by p type Al
0.3Ga
0.7The thickness that N makes is the p type current barrier layer 106 of 20nm, by p type Al
0.05Ga
0.95The thickness that N makes is the p type covering 107 of 0.5 μ m, and is the p type contact layer 108 of 0.1 μ m by the thickness that p type GaN makes, by epitaxial growth with they from Semiconductor substrate 101 with this sequential cascade on the Semiconductor substrate of making by n type GaN 101.At this, the mixed crystal ratio in each of above-mentioned layer is suitably adjusted, and irrelevant with essence of the present invention.According to the mixed crystal ratio of Multiple Quantum Well active layer 105, the wavelength of nitride semi-conductor laser emitted laser that will be from the present embodiment suitably for example, is adjusted in the scope of 370nm-470nm.In the present embodiment, Wavelength of Laser is set at 405nm.
Be formed on the nitride semi-conductor laser 100 in the present embodiment, the mode of formation is that part is removed p type covering 107 and p type contact layer 108, makes striated vallum line part 111 extend on the cavity length direction.At this, the width of fringe of vallum line part 111 is for example about 1.2-2.4 μ m, typically about 1.5 μ m.
P-electrode 110 is made by the multilayer at lip-deep Pd layer, Mo layer and the Au layer of p type contact layer 108.Part below p electrode 110 except that the part that forms vallum line part 111 is settled by SiO
2Layer and TiO
2The dielectric film 109 that the multilayer of layer is made.In addition, on n type GaN substrate 101 and a side opposite surfaces stacked above-mentioned layer, form the n-electrode of making by the multilayer of Hf layer and Al layer 112.
Fig. 2 is the end view of nitride semi-conductor laser on the cavity length direction that schematically shows in the present embodiment shown in Figure 1.At this, on the facet 113 of nitride semi-conductor laser 100 emission side in the present embodiment, what form thickness and be 6nm films 114, describedly films 114 by forming structural formula Al
aO
bN
cThe aluminium oxynitride of (a+b+c=1,0＜b≤0.35) expression is made.To form thickness on 114 be the pellumina 115 of 80nm filming.At this, in above-mentioned composition structural formula, Al represents that aluminium, O represent oxygen, and N represents nitrogen.In addition, in above-mentioned composition structural formula, a represents the composition ratio of aluminium, and b represents the composition ratio of oxygen, and c represents the composition ratio of nitrogen.Forming under the situation of filming, can comprise argon to a certain degree by sputter.Yet,, do not comprising on the basis of argon except that Al, O and N etc. the expression composition ratio at this.In other words, the composition ratio of Al, O and N adds up to 1.
In addition, on the facet 116 of the light reflection side of the nitride semi-conductor laser 100 in the present embodiment, forming thickness in the following order is the aluminium oxynitride film 117 of 6nm, and thickness is pellumina 118 and the highly reflecting films 119 of 80nm.Form highly reflecting films 119 by the following method: the oxidation titanium film that silicon oxide film that stacked four pairs of thickness are 71nm and thickness are 46nm (begin from silicon oxide film stacked), forming thickness afterwards on outmost surface is the silicon oxide film of 142nm.
On the facet 113 and facet 116 of the sample that is prepared as follows, form respectively and aforesaidly film 114, pellumina 115, aluminium oxynitride film 117, pellumina 118 and highly reflecting films 119: will be by on above-mentioned Semiconductor substrate, stacking gradually above-mentioned nitride semiconductor layer such as resilient coating, form vallum line part, form dielectric film afterwards, p-electrode and n-electrode and the wafer cleavage that forms are to expose facet 113 and facet 116 as cleaved surface.
Forming above-mentioned filming before 114,,,, remove attached to oxidation film on the facet 113 or impurity for example being equal to or higher than heating facet 113 under 100 ℃ the temperature by in precipitation equipment preferably in order to clean.Yet, can not carry out this cleaning in the present invention.Alternatively, can clean facet 113 by with argon or nitrogen plasma irradiation facet 113.Yet, can not carry out this cleaning in the present invention.Can in heating facet 113, use plasma radiation.For aforesaid plasma radiation, for example, also can use argon plasma, continue to use nitrogen plasma afterwards.Can be with the opposite plasma that uses in order.Except that argon and nitrogen, for example, can also use the rare gas as helium, neon, xenon or krypton.
Can be by for example ECR (electron cyclotron resonace) sputter as described below, forms and above-mentionedly film 114, perhaps can evaporate etc. by any other sputter, CVD (chemical vapour deposition (CVD)), EB (electron beam), form and above-mentionedly film 114.
Fig. 3 has shown a kind of structure of exemplary ECR sputter deposition apparatus.At this, the ECR sputter deposition apparatus comprises settling chamber 200, and solenoid 203 and microwave are introduced window 202.Settling chamber 200 disposes gas access 201 and gas vent 209.In settling chamber 200, be mounted with: be connected to the Al target 204 of RF power supply 208, and be mounted with heater 205.In settling chamber 200, be mounted with sample stage 207.Aforesaid sample 206 is placed on the sample stage 207.At this, settle solenoid 203 to be used to produce the essential magnetic field of plasma with generation.RF power supply 208 is used for sputter Al target 204.In addition, microwave 210 is introduced window 202 by microwave and be incorporated into settling chamber 200.
Then, from the gas access 201, the flow velocity of nitrogen with 5.2sccm is incorporated in the settling chamber 200, introduces oxygen, and introduce argon gas, producing plasma effectively, thereby improve deposition rate with the flow velocity of 20.0sccm with the flow velocity of 1.0sccm.At this,, can change the oxygen content of filming in 114 above-mentioned by changing nitrogen in settling chamber 200 and the ratio between the oxygen.In addition, Al target 204 is applied the RF power of 500W, with sputter Al target 204.If use to produce the microwave power of the essential 500W of plasma, then can with
/ second deposition rate form and to film 114 by what aluminium oxynitride was made, described filming 114 is that the light of 405nm has 2.1 refractive index for wavelength.Can measure constitute the content separately (atom %) of film 114 aluminium, nitrogen and oxygen by for example AES (Auger electron spectroscopy).Can also measure constitute the content of 114 the oxygen of filming by TEM-EDX (transmission electron microscope-energy dispersive X-ray spectrum).
By AES, at the composition of analyzing the aluminium oxynitride that under condition same as described above, prepares respectively on the thickness direction.As a result, find that aluminium oxynitride has roughly composition uniformly on thickness direction, wherein aluminium content is 34.8 atom %, and oxygen content is that 3.8 atom % and nitrogen content are 61.4 atom %.At this, also detect the argon of minute quantity.At this, because absorbed the part argon gas that is incorporated into the settling chamber 200 that is used for sputter Al target 204, so there is argon.When all atom aggregates of film aluminium, oxygen, nitrogen and argon in 100 are 100 atom %, filming argon content in 114 in greater than 0 atom % and scope less than 5 atom %.Argon content normally approximates or is higher than 1 atom %, and is equal to or less than 3 atom %, but the invention is not restricted to this.
In addition, can also be similar to and above-mentionedly film 114, be formed on the pellumina 115 of emission side and at aluminium oxynitride film 117, pellumina 118 and the highly reflecting films 119 of light reflection side by the ECR sputter.Preferably, before forming these films, also use the cleaning of heating and/or the cleaning of use plasma radiation.At this, remarkable in the degeneration of the luminous component of the high emission side of optical density, and compare with emission side, not remarkable usually in the degeneration of the low light reflection side of optical density.Therefore, in the present invention, on the facet 116 of light reflection side, can not settle the film as the aluminium oxynitride film.At this, in the present embodiment, forming thickness on the facet 116 of light reflection side is the aluminium oxynitride film 117 of 6nm.Yet, the thickness of aluminium oxynitride film 117 can be increased to for example 50nm.
In addition, carry out heat treated after above-mentioned film can be formed on facet.This can expect and removes the moisture that comprises and improve film quality in above-mentioned film.
By this way, on the facet 113 of the emission side of above-mentioned sample, form in the following order and film 114 and pellumina 115, and on the facet 116 of light reflection side, form aluminium oxynitride film 117, pellumina 118 and highly reflecting films 119 in the following order.Afterwards, sample is divided into small pieces, thereby obtains the nitride semi-conductor laser in the present embodiment.
Fig. 4 has shown near the TEM photo of the nitride semi-conductor laser in the present embodiment facet of emission side.Fig. 5 has shown the image K-M at the TEM of the regional A shown in Fig. 4, and Fig. 6 has shown the image K-M at the TEM of the area B shown in Fig. 4.The area B that shows in Fig. 4 extends across two zones, promptly at the facet 113 of emission side with film 114.In Fig. 6, reduce spot size and distinguish mutually with diffraction image with these two zones.
As shown in Figure 5, because in this diffraction image, diffraction spot is dispersed, it should be understood that the part of 114 the regional A of filming that is made by aluminium oxynitride is crystallization.
At this, the arrow shown in Fig. 6 is illustrated in 114 the diffraction spot of filming in the area B.As shown in Figure 6, film 114 diffraction spot is almost consistent with the diffraction spot of the nitride semiconductor crystal of the facet 113 that is formed on emission side.Therefore, the crystallographic axis of nitride semiconductor crystal of determining to be formed on the facet 113 of emission side is to align with the film crystallographic axis of 114 aluminium oxynitride crystal of formation.
At this, strictly speaking, Fig. 6 is without comparison at the luminous component of the nitride semi-conductor laser of the present embodiment and the diffraction spot between 114 of filming.Yet because be to go out the facet of the wafer that nitride semiconductor layer forms by epitaxial growth successively at the facet 113 of emission side, so can suppose, the crystallographic axis of all nitride semiconductor crystals that is formed on the facet 113 of luminous component aligns.Therefore, the crystallographic axis that can suppose the nitride semiconductor crystal that forms the luminous component part of the facet 113 of the nitride semi-conductor laser emission side of the present embodiment (promptly) is to align with the film crystallographic axis of 114 aluminium oxynitride crystal of formation.
In Fig. 6,114 the diffraction spot of filming is almost consistent with the diffraction spot of the nitride semiconductor crystal of the facet 113 that is formed on emission side.Yet, differ from one another aspect lattice constant because be formed on film 114 aluminium oxynitride crystal of the nitride semiconductor crystal and form of the facet 113 of emission side, so the position of these diffraction spots of conversion to a certain extent.In addition, at the mid portion of Fig. 6, the diffraction spot of nitride semiconductor crystal that is formed on the facet 113 of emission side seems to seem that size is big and has hidden 114 the diffraction spot of filming.
Table 1 has shown the result of the plan range on each direction that forms 114 the aluminium oxynitride crystal of filming, and described result obtains from 114 the diffraction spot of filming shown in Fig. 5.As a reference, plan range at the aluminum nitride crystal shown in the JCPD card also has been described.At this, the plan range on 114 the C direction of principal axis of filming that in the present embodiment, prepares be 2.48 dusts (
).
(table 1)
In addition, in the crystallographic system of the pellumina 115 on 114 of filming, and find that it is an amorphous by tem observation.
Nitride semi-conductor laser in mensuration the present embodiment is respectively before wearing out and in aging (70 ℃, CW drives, luminous power 100mW) COD level afterwards.The results are shown among Fig. 7.As shown in Figure 7, the COD level before aging is about 400mW, even and after 400 hours ageing time, the COD level also reduces hardly.
Reason can be supposed as follows.In the nitride semi-conductor laser of the present embodiment, form 114 the aluminium oxynitride crystal of filming and have so high crystallinity, so that look like on the nitride semiconductor crystal of the facet 113 that is formed on emission side epitaxially grown.Film with the amorphous that is considered to comprise many defectives and to compare, this high crystalline film plays a part to suppress the transmission of oxygen effectively.
In the above description, can form by forming structural formula Al by reactive sputtering
aO
bN
cWhat the aluminium oxynitride of (a+b+c=1,0＜b≤0.35) expression was made films 114, and described reactive sputtering uses by forming structural formula Al
xO
yThe target that the aluminium oxide of (0＜x＜1,0＜y＜0.6) is made replaces at the Al target 204 shown in Fig. 3, and nitrogen is incorporated in the settling chamber 200.In the case, even be not intentionally oxygen etc. to be incorporated in the settling chamber 200, also can form and film 114.Because aluminium is oxidable relatively, so, then be difficult to control and reproduce 114 the composition of filming with low oxygen content if introduce oxygen.Yet, if will be by forming structural formula Al
xO
yThe aluminium oxide of (0＜x＜1,0＜y＜0.6) expression is used for target and under the situation of not introducing oxygen, only nitrogen is incorporated in the settling chamber 200, then can relatively easily form have a low oxygen content film 114.At this, can use the target of making by the aluminium oxynitride that comprises low oxygen content to reach similar effects.
Attention is under the situation of using the reactive sputtering device, even do not use the target of making by aluminium oxide, also can be by the following method, preparation has the target of aluminium oxide on the surface of target made of aluminum: settle the target of being made by alundum (Al in the settling chamber, under the situation of introducing oxygen, apply microwave to produce oxygen plasma, make the surface of the target that the oxygen plasma oxidation made by alundum (Al then.
Alternatively, as follows 1 and step 2, can also use target made of aluminum to form the aluminium oxynitride film.
Step 1
Oxygen is incorporated in the settling chamber of reactive sputtering device, described reactive sputtering device is included in wherein the target of settling made of aluminum, produces oxygen plasma applying under the situation of microwave.Target made of aluminum is exposed in the oxygen plasma, make in the degree of depth of several approximately nm in surface of target made of aluminum with aluminaization.Thereby on the surface of target made of aluminum, form the target of making by aluminium oxide.
Step 2
Afterwards, be incorporated into nitrogen and argon gas in the settling chamber and applying under the situation of microwave, make it become plasmoid.Then, sputter at the target of making by aluminium oxide of step 1 preparation.Thereby can form the aluminium oxynitride film.
At this, in the above description, can between step 1 and step 2, provide following steps in addition: the surface of nitride-based semiconductor is exposed in the plasma of admixture of gas of argon gas, nitrogen or argon gas and nitrogen.
(second embodiment)
Nitride semi-conductor laser in the present embodiment has with nitride semi-conductor laser in the first embodiment similarly constructs, difference is: the structure that has changed the film that forms on the structure of the film that forms on the facet 113 of emission side and the facet 116 in the light reflection side.
In the nitride semi-conductor laser of the present embodiment, what form the thickness of being made by aluminium nitride and be 20nm on the facet 113 of emission side films 114, and to form thickness on 114 be the pellumina 115 of 200nm filming.
Forming thickness on the facet 116 of light reflection side is the aluminium nitride film of 12nm, forming thickness on described aluminium nitride film is the pellumina of 80nm, and on described pellumina, form highly reflecting films by the following method: the oxidation titanium film that silicon oxide film that stacked four pairs of thickness are 81nm and thickness are 54nm (begin from silicon oxide film stacked), afterwards, forming thickness on outmost surface is the silicon oxide film of 162nm.
At this, be similar to first embodiment, by TEM image K-M 114 the crystallographic system of determining to film.Discovery is filmed and 114 is formed by aluminum nitride crystal.Based on the TEM image K-M, find that also the crystallographic axis that forms 114 the aluminum nitride crystal of filming is to align with the nitride semiconductor crystal of the facet 113 that is formed on emission side.
For the nitride semi-conductor laser in the present embodiment, be similar to first embodiment, also measure in aging (70 ℃, CW drives, luminous power 100mW) COD level afterwards.As a result, even find that after aging 400 hours, the COD level of the nitride semi-conductor laser in the present embodiment also reduces hardly.
(the 3rd embodiment)
Nitride semi-conductor laser in the present embodiment has with nitride semi-conductor laser in the first embodiment similarly constructs, difference is: the structure that has changed the film that forms on the structure of the film that forms on the facet 113 of emission side and the facet 116 in the light reflection side.
In the nitride semi-conductor laser of the present embodiment, what form thickness and be 40nm on the facet 113 of emission side films 114, describedly films 114 by forming structural formula Al
0.33O
0.11N
0.56Aluminium oxynitride make, and to form thickness on 114 be the pellumina 115 of 240nm filming.
Forming thickness on the facet 116 of light reflection side is the aluminium nitride film of 12nm, forming thickness on described aluminium nitride film is the pellumina of 80nm, and on described pellumina, form highly reflecting films by the following method: the oxidation titanium film that silicon oxide film that stacked four pairs of thickness are 81nm and thickness are 54nm (begin from silicon oxide film stacked), afterwards, forming thickness on outmost surface is the silicon oxide film of 162nm.
At this, be similar to first embodiment, by TEM image K-M 114 the crystallographic system of determining to film.Discovery is filmed and 114 is formed by the aluminium oxynitride crystal.Based on the TEM image K-M, find that also the crystallographic axis that forms 114 the aluminium oxynitride crystal of filming is to align with the nitride semiconductor crystal of the facet 113 that is formed on emission side.
For the nitride semi-conductor laser in the present embodiment, be similar to first embodiment, also measure in aging (70 ℃, CW drives, luminous power 100mW) COD level afterwards.As a result, even find that after aging 400 hours, the COD level of the nitride semi-conductor laser in the present embodiment also reduces hardly.
(the 4th embodiment)
Nitride semi-conductor laser in the present embodiment has with nitride semi-conductor laser in the first embodiment similarly constructs, difference is: the structure that has changed the film that forms on the facet 113 of emission side, with the structure of the film that forms on the facet 116 of light reflection side, and the emission Wavelength of Laser is 460nm.
In the nitride semi-conductor laser of the present embodiment, on the facet 113 of emission side, what only form the thickness of being made by aluminium oxynitride and be 50nm films 114, and wherein reflectivity is about 10%.
Forming thickness on the facet 116 of light reflection side is the aluminium oxynitride film of 6nm, forming thickness on described aluminium oxynitride film is the pellumina of 80nm, and on described pellumina, form highly reflecting films by the following method: the oxidation titanium film that silicon oxide film that stacked four pairs of thickness are 81nm and thickness are 54nm (begin from silicon oxide film stacked), afterwards, forming thickness on outmost surface is the silicon oxide film of 162nm.
At this, be similar to first embodiment, by TEM image K-M 114 the crystallographic system of determining to film.Discovery is filmed and 114 is formed by the aluminium oxynitride crystal.Based on the TEM image K-M, find that also the crystallographic axis that forms 114 the aluminium oxynitride crystal of filming is to align with the nitride semiconductor crystal of the facet 113 that is formed on emission side.
For the nitride semi-conductor laser in the present embodiment, be similar to first embodiment, also measure in aging (70 ℃, CW drives, luminous power 100mW) COD level afterwards.As a result, even find that after aging 400 hours, the COD level of the nitride semi-conductor laser in the present embodiment also reduces hardly.
(the 5th embodiment)
Nitride semi-conductor laser in the present embodiment has with nitride semi-conductor laser in the first embodiment similarly constructs, difference is: the structure that has changed the film that forms on the structure of the film that forms on the facet 113 of emission side and the facet 116 in the light reflection side.
In the nitride semi-conductor laser of the present embodiment, what form thickness and be 50nm on the facet 113 of emission side films 114, describedly films 114 by forming structural formula Al
0.30O
0.25N
0.45Aluminium oxynitride make, and to form thickness on 114 be the silicon nitride film of 110nm filming.
In addition, forming thickness on the facet 116 of light reflection side is the aluminium oxynitride film of 50nm.Forming thickness on described aluminium oxynitride film is the silicon oxide film of 50nm.On described silicon oxide film, form highly reflecting films by the following method: the silicon nitride film that silicon oxide film that stacked six pairs of thickness are 71nm and thickness are 50nm (begin from silicon oxide film stacked), afterwards, forming thickness on outmost surface is the silicon oxide film of 142nm.
Silicon nitride film ratio silicon oxide film is moisture-resistant more, and has lower oxygen permeability (in other words, and compare in silicon oxide film, O-H group and oxygen more can not spread).Therefore, silicon nitride film the formation on 114 of filming improved suppress since the transmission of oxygen cause, in the possibility of the oxidation of the facet 113 of emission side.
At this, be preferably 5nm or thicker at the thickness of the silicon nitride film on 114 of filming, and 80nm or thicker more preferably.If less than 5nm, then may be difficult to film is deposited in 114 the surface of filming equably at the thickness of the silicon nitride film on 114 of filming.If thicker, then can increase the effect that suppresses the oxygen diffusion than 80nm.
At this, be similar to first embodiment, by TEM image K-M 114 the crystallographic system of determining to film.Discovery is filmed and 114 is formed by the aluminium oxynitride crystal.Based on the TEM image K-M, find that also the crystallographic axis that forms 114 the aluminium oxynitride crystal of filming is to align with the nitride semiconductor crystal of the facet 113 that is formed on emission side.
For the nitride semi-conductor laser in the present embodiment, be similar to first embodiment, also measure in aging (70 ℃, CW drives, luminous power 100mW) COD level afterwards.As a result, even find that after aging 400 hours, the COD level of the nitride semi-conductor laser in the present embodiment also reduces hardly.
(the 6th embodiment)
Nitride semi-conductor laser in the present embodiment has with nitride semi-conductor laser in the first embodiment similarly constructs, difference is: the structure that has changed the film that forms on the structure of the film that forms on the facet 113 of emission side and the facet 116 in the light reflection side.
In the nitride semi-conductor laser of the present embodiment, what form thickness and be 30nm on the facet 113 of emission side films 114, describedly films 114 by forming structural formula Al
0.31O
0.03N
0.66Aluminium oxynitride make, to form thickness on 114 be the silicon nitride film of 140nm filming, and to form thickness on described silicon nitride film be the silicon oxide film of 140nm.At this, film on 114 silicon nitride film and be preferably 5nm or thicker at the silicon oxide film thickness separately of described silicon nitride film.If these films thickness separately less than 5nm, then may be difficult to film is deposited in the surface equably.
In addition, forming thickness on the facet 116 of light reflection side is the aluminium oxynitride film of 50nm.Forming thickness on described aluminium oxynitride film is the silicon oxide film of 50nm.On described silicon oxide film, form highly reflecting films by the following method: the silicon nitride film that silicon oxide film that stacked six pairs of thickness are 71nm and thickness are 50nm (begin from silicon oxide film stacked), afterwards, forming thickness on outmost surface is the silicon oxide film of 142nm.
At this, be similar to first embodiment, by TEM image K-M 114 the crystallographic system of determining to film.Discovery is filmed and 114 is formed by the aluminium oxynitride crystal.Based on the TEM image K-M, find that also the crystallographic axis that forms 114 the aluminium oxynitride crystal of filming is to align with the nitride semiconductor crystal of the facet 113 that is formed on emission side.
For the nitride semi-conductor laser in the present embodiment, be similar to first embodiment, also measure in aging (70 ℃, CW drives, luminous power 100mW) COD level afterwards.As a result, even find that after aging 400 hours, the COD level of the nitride semi-conductor laser in the present embodiment also reduces hardly.
In addition, at thickness is the pellumina replacement silicon oxide film of 140nm, as the nitride semi-conductor laser in the present embodiment under the situation of the outmost surface layer of facet 113 sides of emission side, also measure as mentioned above at aging (70 ℃, CW drives, luminous power 100mW) afterwards COD level.As a result, find that as in the above description, even after aging 400 hours, the COD level is reduction hardly also.
(the 7th embodiment)
Nitride semi-conductor laser in the present embodiment has with nitride semi-conductor laser in the first embodiment similarly constructs, difference is: the structure that has changed the film that forms on the structure of the film that forms on the facet 113 of emission side and the facet 116 in the light reflection side.
In the nitride semi-conductor laser of the present embodiment, what form thickness and be 30nm on the facet 113 of emission side films 114, describedly films 114 by forming structural formula Al
0.32O
0.08N
0.60Aluminium oxynitride make, to form thickness on 114 be the silicon nitride film of 140nm filming, and to form thickness on described silicon nitride film be the pellumina of 160nm.
In addition, forming thickness on the facet 116 of light reflection side is the aluminium oxynitride film of 50nm.Forming thickness on described aluminium oxynitride film is the silicon oxide film of 50nm.On described silicon oxide film, form highly reflecting films by the following method: the silicon nitride film that silicon oxide film that stacked six pairs of thickness are 71nm and thickness are 50nm (begin from silicon oxide film stacked), afterwards, forming thickness on outmost surface is the silicon oxide film of 142nm.
At this, be similar to first embodiment, by TEM image K-M 114 the crystallographic system of determining to film.Discovery is filmed and 114 is formed by the aluminium oxynitride crystal.Based on the TEM image K-M, find that also the crystallographic axis that forms 114 the aluminium oxynitride crystal of filming is to align with the nitride semiconductor crystal of the facet 113 that is formed on emission side.
For the nitride semi-conductor laser in the present embodiment, be similar to first embodiment, also measure in aging (70 ℃, CW drives, luminous power 100mW) COD level afterwards.As a result, even find that after aging 400 hours, the COD level of the nitride semi-conductor laser in the present embodiment also reduces hardly.
In addition, at thickness is the silicon oxide film replacement pellumina of 140nm, as the nitride semi-conductor laser in the present embodiment under the situation of the outmost surface layer of facet 113 sides of emission side, also measure as mentioned above at aging (70 ℃, CW drives, luminous power 100mW) afterwards COD level.As a result, find that as in the above description, even after aging 400 hours, the COD level is reduction hardly also.
(the 8th embodiment)
Nitride semi-conductor laser in the present embodiment has with nitride semi-conductor laser in the first embodiment similarly constructs, difference is: the structure that has changed the film that forms on the structure of the film that forms on the facet 113 of emission side and the facet 116 in the light reflection side.
In the nitride semi-conductor laser of the present embodiment, what form thickness and be 60nm on the facet 113 of emission side films 114, describedly films 114 by forming structural formula Al
0.32O
0.08N
0.60Aluminium oxynitride make, and to form thickness on 114 be the oxygen silicon nitride membrane of 230nm filming.At this, at the oxygen silicon nitride membrane on 114 of filming by forming structural formula Si
0.348O
0.04N
0.612Expression.Silicone content is 34.8 atom %, and oxygen content is that 4.0 atom % and nitrogen content are 61.2 atom %.
In addition, forming thickness on the facet 116 of light reflection side is the aluminium oxynitride film of 50nm.Forming thickness on described aluminium oxynitride film is the silicon oxide film of 50nm.On described silicon oxide film, form highly reflecting films by the following method: the silicon nitride film that silicon oxide film that stacked six pairs of thickness are 71nm and thickness are 50nm (begin from silicon oxide film stacked), afterwards, forming thickness on outmost surface is the silicon oxide film of 142nm.
At this, be similar to first embodiment, by TEM image K-M 114 the crystallographic system of determining to film.Discovery is filmed and 114 is formed by the aluminium oxynitride crystal.Based on the TEM image K-M, find that also the crystallographic axis that forms 114 the aluminium oxynitride crystal of filming is to align with the nitride semiconductor crystal of the facet 113 that is formed on emission side.
For the nitride semi-conductor laser in the present embodiment, be similar to first embodiment, also measure in aging (70 ℃, CW drives, luminous power 100mW) COD level afterwards.As a result, even find that after aging 400 hours, the COD level of the nitride semi-conductor laser in the present embodiment also reduces hardly.
(the 9th embodiment)
Nitride semi-conductor laser in the present embodiment has with nitride semi-conductor laser in the first embodiment similarly constructs, difference is: the structure that has changed the film that forms on the structure of the film that forms on the facet 113 of emission side and the facet 116 in the light reflection side.
In the nitride semi-conductor laser of the present embodiment, what form thickness and be 40nm on the facet 113 of emission side films 114, describedly films 114 by forming structural formula Al
0.32O
0.08N
0.60Aluminium oxynitride make, and to form thickness on 114 be the zirconium oxide film of 100nm filming.
In addition, forming thickness on the facet 116 of light reflection side is the aluminium oxynitride film of 50nm.Forming thickness on described aluminium oxynitride film is the silicon oxide film of 50nm.On described silicon oxide film, form highly reflecting films by the following method: the silicon nitride film that silicon oxide film that stacked six pairs of thickness are 71nm and thickness are 50nm (begin from silicon oxide film stacked), afterwards, forming thickness on outmost surface is the silicon oxide film of 142nm.
At this, be similar to first embodiment, by TEM image K-M 114 the crystallographic system of determining to film.Discovery is filmed and 114 is formed by the aluminium oxynitride crystal.Based on the TEM image K-M, find that also the crystallographic axis that forms 114 the aluminium oxynitride crystal of filming is to align with the nitride semiconductor crystal of the facet 113 that is formed on emission side.
For the nitride semi-conductor laser in the present embodiment, be similar to first embodiment, also measure in aging (70 ℃, CW drives, luminous power 100mW) COD level afterwards.As a result, even find that after aging 400 hours, the COD level of the nitride semi-conductor laser in the present embodiment also reduces hardly.
(the tenth embodiment)
Nitride semi-conductor laser in the present embodiment has with nitride semi-conductor laser in the first embodiment similarly constructs, difference is: the structure that has changed the film that forms on the structure of the film that forms on the facet 113 of emission side and the facet 116 in the light reflection side.
In the nitride semi-conductor laser of the present embodiment, what form the thickness of being made by aluminium nitride and be 50nm on the facet 113 of emission side films 114, and to form thickness on 114 be the silicon nitride film of 140nm filming.
In addition, forming thickness on the facet 116 of light reflection side is the aluminium nitride film of 50nm.Forming thickness on described aluminium nitride film is the silicon oxide film of 50nm.On described silicon oxide film, form highly reflecting films by the following method: the silicon nitride film that silicon oxide film that stacked six pairs of thickness are 71nm and thickness are 50nm (begin from silicon oxide film stacked), afterwards, forming thickness on outmost surface is the silicon oxide film of 142nm.
At this, be similar to first embodiment, by TEM image K-M 114 the crystallographic system of determining to film.Discovery is filmed and 114 is formed by aluminum nitride crystal.Based on the TEM image K-M, find that also the crystallographic axis that forms 114 the aluminum nitride crystal of filming is to align with the nitride semiconductor crystal of the facet 113 that is formed on emission side.
For the nitride semi-conductor laser in the present embodiment, be similar to first embodiment, also measure in aging (70 ℃, CW drives, luminous power 100mW) COD level afterwards.As a result, even find that after aging 400 hours, the COD level of the nitride semi-conductor laser in the present embodiment also reduces hardly.
As in the nitride semi-conductor laser of the present embodiment, on the facet 113 that forms by nitride semiconductor crystal in emission side, formation films 114 by what aluminum nitride crystal was made, described filming 114 is such crystallizations, wherein under crystallographic axis and the situation that the nitride semiconductor crystal of the facet 113 that is formed on emission side aligns, consider the raising reliability, be preferably silicon nitride film, oxygen silicon nitride membrane or aluminium oxynitride film at the film that forms on 114 of filming, rather than the film of making by oxide.
In addition, the facet of the nitride semi-conductor laser in the present embodiment is partly carried out visual examination (after being divided into small pieces, by stereoscope etc., observing the state of peeling off of the film that forms on the facet of nitride semi-conductor laser).At this, discovery is in the nitride semi-conductor laser of the present embodiment, compare with the nitride semi-conductor laser that is included in the pellumina that forms on 114 by filming of making of aluminium nitride in second embodiment, can reduce peeling off of the film that on the facet of emission side, forms.
At this, when filming of being made by aluminium nitride formed the film of being made by oxide on 114,88% in all do not suffer that film peels off (hereinafter referred to as " with respect to the yield of stripping film ").When filming of being made by aluminium nitride film forms the film of being made by nitride or oxynitride on 114, it is 94% in all with respect to the yield of stripping film.
In being divided into the process of small pieces, for example in the zone of representing by C in the nitride semi-conductor laser shown in the schematic cross-section in Figure 10, peeling off of this film often taken place.Peeling off in subsequently installation step and/or ageing test of this film further develops, thereby causes defective.Should point out that the nitride semi-conductor laser shown in Figure 10 has that current blockade uses by SiO
2Layer and TiO
2The p-lateral electrode 79 that dielectric film 78 that the multilayer of layer is made and injection current are used.
Consider above-mentioned, under 114 situations about making of filming, at the film that forms on 114 more preferably nitride or the oxynitride of filming by aluminium nitride.Under 114 situations about making of filming by aluminium oxynitride, do not observe any difference with respect to the yield of stripping film, this can be owing to as mentioned above in the difference of the material of the film on 114 of filming.Therefore, can think, form 114 the aluminium oxynitride of filming and to reduce difference aspect thermal coefficient of expansion and internal stress.
In addition, in the method for first to the tenth embodiment,, can improve the yield in the facet of above-mentioned nitride semi-conductor laser with respect to stripping film by making dielectric film 109 shown in Fig. 1 that current blockade uses and the dielectric film 78 shown in Figure 10.
In nitride semi-conductor laser, near peeling off of the film vallum line part is the most remarkable.Discovery when the dielectric film that forms on vallum line part next door contacts with the film that forms, can be suppressed near peeling off of the film of vallum line part effectively on facet.This may be because reduced distortion at dielectric film with the part that the film that forms contacts on facet.At this, if dielectric film does not contact with the film that forms on facet, 60% in then being reduced to approximately all with respect to the yield of stripping film.
The dielectric film of formation comprises by vallum line part, for example the film of being made by following material: oxide (oxides of silicon, zirconium, tantalum, yttrium, hafnium, aluminium, gallium etc.), nitride (nitride of aluminium, silicon etc.) or oxynitride (oxynitrides of aluminium, silicon etc.).
Should point out, although in above-mentioned first to the tenth embodiment, the width of fringe that vallum line part 111 has been described is about 1.2-2.4 μ m, but the present invention suitably can also be applied to illuminating wide area-type nitride semi-conductor laser (wherein the width of fringe of vallum line part 111 is about 2-100 μ m).
In above-mentioned first to the tenth embodiment, 114 the formation temperature of filming preferably is equal to or higher than 200 ℃.In this case, can improve the film crystallinity of 114 aluminium oxynitride crystal of aluminum nitride crystal or formation.
If as in first to the tenth embodiment, formation films 114 after making electrode structure and current blockade structure, then considers to prevent breaking of these structures, 114 the formation temperature of filming preferably is equal to or less than 500 ℃.
As mentioned above, film 114 for what form at luminous component, described luminous component is made by the nitride semiconductor crystal of nitride semi-conductor laser, not only when using aluminium nitride, and when use contains oxygen material such as aluminium oxynitride, can make these material crystallizations, make the crystallographic axis of aluminum nitride crystal or aluminium oxynitride crystal align with the nitride semiconductor crystal of luminous component, thereby improve the COD level of nitride semi-conductor laser, and prevent that effectively luminous component is through degenerating for a long time.
At this, in above-mentioned first to the tenth embodiment, use n type GaN substrate as Semiconductor substrate 101.The invention is characterized in, form by what aluminum nitride crystal or aluminium oxynitride crystal were made at the luminous component of making by nitride semiconductor crystal and to film 114, described aluminum nitride crystal or aluminium oxynitride crystal have the crystallographic axis that aligns with the nitride semiconductor crystal of luminous component, thereby improve the reliability of nitride semi-conductor laser.Therefore, by forming structural formula Al
sGa
tThe substrate that the nitride system semiconductor of N (s+t=1,0≤s≤1,0≤t≤1) expression becomes is preferably used as Semiconductor substrate 101.Consider and reduce and film 114 lattice mismatch and reduce defective or distortion, preferably will comprise the nitride-based semiconductor substrate of aluminium, as AlN substrate or AlGaN substrate as Semiconductor substrate 101.
In above-mentioned first to the tenth embodiment,, make nitride semi-conductor laser by nitride semiconductor layer being stacked gradually on the Semiconductor substrate that becomes by nitride system semiconductor.Growing surface according to the nitride semiconductor layer of Semiconductor substrate 101, the surface state of change stacked nitride semiconductor layer on the growing surface of Semiconductor substrate 101, and can change 114 the crystallinity of filming that on the side surface of nitride semiconductor layer, forms.Thereby find that the growing surface of the Semiconductor substrate 101 of nitride semi-conductor laser can influence 114 the crystallinity of filming.At this, the growing surface of the nitride semiconductor layer of the Semiconductor substrate 101 that is become by nitride system semiconductor is preferably C-plane { 0001}, A-plane { 11-20}, R-plane { 1-102} or M-plane { 1-100}, and any one oblique angle of growing surface and these crystal faces is preferably in 2 °.
Although be noted that any given numeral crystrallographic plane or the direction that should use line expression basically, because expression is limited, in this manual, it is used in "-" expression of any given digital front, and replacement is represented by last line.
In addition, in above-mentioned first to the 3rd embodiment, form pellumina 115 on 114 with the control reflectivity filming.Alternatively, can form and for example be selected from least a in following: oxidation film, as pellumina, silicon oxide film, oxidation titanium film, hafnium oxide film, zirconium oxide film, niobium oxide film, tantalum-oxide film or yittrium oxide film; Nitride film such as aluminium nitride film or silicon nitride film; And have oxynitride film such as aluminium oxynitride film or an oxygen silicon nitride membrane with the 114 different compositions of filming.Alternatively, can not form film on 114 filming.Alternatively, can form magnesium fluoride (MgF) film on 114 as the film of making by fluoride filming.
For example, with thickness be the oxygen content of 20nm be the aluminium oxynitride film of 10 atom % as filming 114, and filming to form thickness on 114 be the silicon nitride film of 150nm.Because as mentioned above, silicon nitride film moisture-resistant, and have low oxygen permeability is so in that film formed filming forms silicon nitride film on 114 by aluminium oxynitride, can suppress because the oxidation of the luminous component that the transmission of oxygen causes.
In the present invention, be under the situation of nitride semiconductor diode device at nitride semiconductor photogenerator, on the light-emitting area (light is drawn the surface) of nitride semiconductor diode device, comprise filming of aluminum nitride crystal or aluminium oxynitride crystal.At this, light-emitting area refers to draw the surface of light from the nitride semiconductor diode device, and can be any one of top surface, lower surface and side of nitride semiconductor diode device.To the emission wavelength (light wavelength) of nitride semiconductor diode device without limits, with high emission intensity and the present invention go for wavelength in the ultraviolet range of about 360nm or the wavelength in visible region.In addition, because similar to the above, the crystallographic axis of aluminum nitride crystal of preferably filming or aluminium oxynitride crystal aligns with the crystallographic axis of the nitride semiconductor crystal that forms light-emitting area, and the thickness of filming is preferably 6nm and 150nm at least at the most.For example, in nitride semiconductor diode device of the present invention, what can form thickness and be 6nm comprises filming of aluminium oxynitride crystal, and can form the pellumina that thickness is 80nm thereon.
In the present invention, under the situation about forming of filming, can change oxygen content (oxygen content from luminous component and the interface between filming reduce gradually or increase) in the mode that changes gradually to the outmost surface of filming by the aluminium oxynitride crystal.In fact, oxygen content has to a certain degree variation in filming.Preferably, the oxygen content in filming preferably changes in the scope that is equal to or less than 35 atom %.
(the 11 embodiment)
Fig. 9 is the cross-sectional view that schematically shows an a preferred embodiment conduct exemplary nitride semiconductor crystal tube device in the present invention of MIS type HFET device.At this, MIS type HFET device has following structure: wherein GaN layer 72 and AlGaN layer 73 are stacked gradually on Semiconductor substrate 71.Then, formation source electrode 74 and drain electrode 75 make it be spaced from each other certain distance on AlGaN layer 73.Between source electrode 74 and drain electrode 75, form gate insulating film 77.On gate insulating film 77, form gate electrode 76.At this, each all is the example of the nitride-based semiconductor among the present invention for GaN layer 72 and AlGaN layer 73.
At this, MIS type HFET device in the present embodiment is characterised in that, the film that use is formed by aluminum nitride crystal or aluminium oxynitride crystal is as gate insulating film 77, and described aluminum nitride crystal or aluminium oxynitride crystal have the crystallographic axis that aligns with the nitride semiconductor crystal that forms AlGaN layer 73.Therefore, can prevent leakage current and can improve reliability.At this, the thickness of gate insulating film 77 is for example about 10nm, preferably at 2nm at least and at the most in the scope of 50nm.
As this gate insulating film 77, for example, can use by forming structural formula Al
dO
eN
fThe film that the aluminium oxynitride of (d+e+f=1,0＜e≤0.35) expression is made.In this composition structural formula, d represents the composition ratio of aluminium (Al), and e represents the composition ratio of oxygen (O), and f represents the composition ratio of nitrogen (N).
Can with first embodiment in the 114 similar methods of filming form gate insulating films 77.
The invention provides: even the nitride semiconductor photogenerator that also has enough reliabilities when under high temperature and high power, being driven; Method with the described nitride semiconductor photogenerator of preparation; And nitride semiconductor crystal tube device with reliability of raising.
In addition, the present invention applicable to the nitride semi-conductor laser of partly locating to have window construction at the facet that comprises luminous component (for example, this a kind of structure: wherein, make near the composition of the active layer the facet that is used for GaAs base semiconductor laser spare become even) increasing band gap and improving under the situation of COD level.
Although describe in detail and for example understand the present invention, obviously should understand the present invention is illustrative and exemplary, and does not think restrictively, and the spirit and scope of the present invention only are subjected to the restriction of appended claim clause.
Claims (13)
1. nitride semiconductor photogenerator, described nitride semiconductor photogenerator are included in filming that luminous component forms, and wherein said filming comprises aluminum nitride crystal; And
Described aluminum nitride crystal has the crystallographic axis that aligns with the crystallographic axis of the nitride semiconductor crystal that forms described luminous component.
2. nitride semiconductor photogenerator according to claim 1, wherein said thickness of filming is 6nm and 150nm at least at the most.
3. nitride semiconductor photogenerator according to claim 1 wherein forms the film of being made by oxide, oxynitride or nitride on described filming.
4. nitride semiconductor photogenerator according to claim 3, wherein the described film of being made by oxide on described filming is pellumina, silicon oxide film, oxidation titanium film, hafnium oxide film, zirconium oxide film, niobium oxide film, tantalum-oxide film or yittrium oxide film.
5. nitride semiconductor photogenerator according to claim 3, wherein the described film of being made by oxynitride on described filming is aluminium oxynitride film or oxygen silicon nitride membrane.
6. nitride semiconductor photogenerator according to claim 3, wherein the described film of being made by nitride on described filming is aluminium nitride film or silicon nitride film.
7. nitride semiconductor photogenerator according to claim 1 wherein forms the magnesium fluoride film on described filming.
8. nitride semiconductor photogenerator according to claim 1, wherein said nitride semiconductor photogenerator is a nitride semi-conductor laser, and forms described filming on the facet of the emission side of described nitride semi-conductor laser.
9. nitride semiconductor photogenerator according to claim 8 wherein uses by forming structural formula Al
sGa
tThe substrate that nitride system semiconductor that N represents becomes is as substrate, s+t=1 wherein, 0≤s≤1,0≤t≤1.
10. nitride semiconductor photogenerator according to claim 1, wherein said nitride semiconductor photogenerator is the nitride semiconductor LED device, and forms described filming on the light-emitting area of described nitride semiconductor LED device.
11. nitride semiconductor photogenerator according to claim 10 wherein uses by forming structural formula Al
sGa
tThe substrate that nitride system semiconductor that N represents becomes is as substrate, s+t=1 wherein, 0≤s≤1,0≤t≤1.
12. a method for preparing the described nitride semiconductor photogenerator of claim 1, described method comprises the steps:
Use argon or the described luminous component of nitrogen plasma irradiation; And
After the irradiation of described plasma, form described aluminum nitride crystal at described luminous component.
13. the method for preparing nitride semiconductor photogenerator according to claim 12, the formation temperature of wherein said aluminum nitride crystal are 200 ℃ at least.
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| US6249534B1 (en) * | 1998-04-06 | 2001-06-19 | Matsushita Electronics Corporation | Nitride semiconductor laser device |
| CN1575533A (en) * | 2001-10-26 | 2005-02-02 | 波兰商艾蒙诺公司 | Nitride semiconductor laser element and manufacturing method thereof |
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| JPH02288287A (en) * | 1989-04-27 | 1990-11-28 | Sharp Corp | Semiconductor laser element |
| JPH03142892A (en) * | 1989-10-27 | 1991-06-18 | Sharp Corp | Semiconductor laser element |
| JPH06291422A (en) * | 1993-04-02 | 1994-10-18 | Canon Inc | Optical semiconductor element |
| JP3184031B2 (en) * | 1993-08-25 | 2001-07-09 | 富士通株式会社 | Optical semiconductor element device and method of manufacturing optical semiconductor device |
| JP3430036B2 (en) * | 1998-10-29 | 2003-07-28 | 松下電器産業株式会社 | Method for forming thin film and method for manufacturing semiconductor light emitting device |
| JP2000196188A (en) * | 1998-12-25 | 2000-07-14 | Toshiba Corp | Semiconductor laser device and manufacture thereof |
| JP2002237648A (en) * | 2001-02-13 | 2002-08-23 | Fuji Photo Film Co Ltd | Semiconductor laser element |
| DE60238195D1 (en) * | 2001-05-31 | 2010-12-16 | Nichia Corp | SEMICONDUCTOR LASER ELEMENT |
| JP2003124560A (en) * | 2001-10-10 | 2003-04-25 | Sharp Corp | End surface aperture semiconductor laser device and manufacturing method therefor |
| US6744076B2 (en) * | 2002-03-14 | 2004-06-01 | The Circle For The Promotion Of Science And Engineering | Single crystalline aluminum nitride film, method of forming the same, base substrate for group III element nitride film, light emitting device and surface acoustic wave device |
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| US6249534B1 (en) * | 1998-04-06 | 2001-06-19 | Matsushita Electronics Corporation | Nitride semiconductor laser device |
| CN1575533A (en) * | 2001-10-26 | 2005-02-02 | 波兰商艾蒙诺公司 | Nitride semiconductor laser element and manufacturing method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101609961A (en) | 2009-12-23 |
| JP2014003314A (en) | 2014-01-09 |
| JP5456752B2 (en) | 2014-04-02 |
| JP5456928B2 (en) | 2014-04-02 |
| CN101043063A (en) | 2007-09-26 |
| CN101499620A (en) | 2009-08-05 |
| CN101499618A (en) | 2009-08-05 |
| CN100568563C (en) | 2009-12-09 |
| CN101499618B (en) | 2012-08-01 |
| CN101609961B (en) | 2012-06-06 |
| CN101499619A (en) | 2009-08-05 |
| JP2012039164A (en) | 2012-02-23 |
| CN101499619B (en) | 2012-07-18 |
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Effective date of registration: 20220322 Address after: Asahi 1, Damen Machi, Fukuyama, Hiroshima, Japan Patentee after: Sharp Fukuyama laser Co.,Ltd. Address before: Japan's Osaka Osaka Abeno Chang Chi Cho 22 No. 22 545-8522 Patentee before: Sharp Corp. |