CN100413086C - Boron phosphide-based compound semiconductor device, production method thereof and light-emitting diode - Google Patents

Boron phosphide-based compound semiconductor device, production method thereof and light-emitting diode Download PDF

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CN100413086C
CN100413086C CNB2003801044473A CN200380104447A CN100413086C CN 100413086 C CN100413086 C CN 100413086C CN B2003801044473 A CNB2003801044473 A CN B2003801044473A CN 200380104447 A CN200380104447 A CN 200380104447A CN 100413086 C CN100413086 C CN 100413086C
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boron phosphide
based compound
compound semiconductor
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CN1717810A (en
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宇田川隆
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Resonac Holdings Corp
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Showa Denko KK
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Abstract

A boron phosphide-based compound semiconductor device with excellent device properties, comprising a boron phosphide-based compound semiconductor layer having a wide bandgap is provided. The boron phosphide-based compound semi-conductor layer consists of an amorphous layer and a polycrystal layer provided to join with the amorphous layer, and the room-temperature bandgap of the boron phosphide-based compound semiconductor layer is from 3.0 eV to less than 4.2 eV.

Description

Boron phosphide-based compound semiconductor device, its manufacture method and light-emitting diode
The cross reference of related application
The application requires the priority of the U.S. Provisional Application 60/432,249 of submission on December 11st, 2002 according to 35U.S.C. § 119 (e) (1).
Technical field
The present invention relates to comprise the boron phosphide-based compound semiconductor device of boron phosphide-based compound semiconductor layer, described layer at room temperature has broad-band gap, the invention still further relates to its manufacture method and light-emitting diode.
Background technology
The III group-III nitride semiconductor, (GaN) is normally used for making nitride compound semiconductor device as gallium nitride, for example light-emitting diode (LED) or laser diode (LD) (referring to for example non-patent literature 1).The known band gap that at room temperature has broad of III group-III nitride semiconductor, and for example, room temperature band gap with the gallium nitride of hexagonal wurtzite (hexagonal wurtzite) structure and aluminium nitride (AlN) reach respectively 3.4eV and 5.9eV (referring to, for example non-patent literature 2).Thereby the III nitride semiconductor layer is used as functional layer, for example the coating of luminescent device or luminescent layer.The III nitride semiconductor layer has such large band gap and helps constructing the junction structure with high potential barrier.For example, disclose a kind of high mobility transistor, comprised the heterojunction of electron supply layer and electron channel layer, described heterojunction is 3.4eV or higher aluminium gallium nitride alloy mixed crystal (Al by utilizing band gap XGa 1-XN:0＜X≤1) constitutes (referring to for example non-patent literature 3).
On the other hand, boron phosphide-based compound semiconductor, for example single boron phosphide (BP) is known as indirect III-V compound semiconductor.
Different with the III group-III nitride semiconductor of for example gallium nitride (GaN), can obtain p type conductive layer easily by specially mixing to boron phosphide-based compound semiconductor.For example, disclose such technology, wherein magnesium (Mg) has been mixed as p type impurity, to obtain p type conductive layer (referring to for example patent documentation 1).Therefore, it is desirable for, can obtain to have the pn knot of barrier potential difference easily by in conjunction with boron phosphide-based compound semiconductor layer and III nitride semiconductor layer with broad-band gap.
Here, for example the room temperature band gap of boron phosphide is known as 2.0eV (referring to for example non-patent literature 2) usually, and, in recent years, developed such technology, wherein, obtained 2.8 to 3.4eV wideer room temperature band gap by optimizing Vapor Growth Conditions or similar approach.Yet, for from boron phosphide-based compound semiconductor layer and III nitride semiconductor layer for example gallium nitride constitute heterojunction with barrier height, the band gap of traditional 2eV that offers boron phosphide is not enough, thereby needs the boron phosphide-based compound semiconductor layer to have wideer band gap.Also not disclose at present such boron phosphide-based compound semiconductor layer, it has broad-band gap and is fit to and wide band gap semiconducter III group-III nitride semiconductor formation heterojunction for example.
(patent documentation 1)
JP-A-2-288388 (terminology used here " JP-A " expression " is not examined disclosed Japanese patent application ")
(non-patent literature 1)
Isamu Akasaki (editor), III Zoku Kagobutsu Handoutai (III compound semiconductor), 1 StEd., Chap.13-14, Baifukan (on December 8th, 1999)
(non-patent literature 2)
Isamu Akasaki (editor), III Zoku Kagobutsu Handoutai (III-V compound semiconductor), 1 StEd., page 150, Baifukan (on May 20th, 1994)
(non-patent literature 3)
Isamu Akasaki (editor), III Zoku Kagobutsu Handoutai (III compound semiconductor), 1 StEd., Chap.6-8, Baifukan (on December 8th, 1999)
Summary of the invention
The present invention produces under such background, thereby, the structure of the boron phosphide-based compound semiconductor layer that an object of the present invention is to be described as follows, described layer has the band gap that is fit to and constitutes heterojunction as the III nitride semiconductor layer of gallium nitride (GaN), it is poor that described heterojunction has suitable barrier height, thereby the boron phosphide-based compound semiconductor device of device performance excellence is provided, and described device comprises the boron phosphide-based compound semiconductor layer with broad-band gap.
The result who carries out broad research in order to address the above problem is boron phosphide-based compound semiconductor device, its manufacture method and light-emitting diode below the inventor has invented.
Especially, the present invention includes:
(1) a kind of boron phosphide-based compound semiconductor device, comprise the boron phosphide-based compound semiconductor layer, described boron phosphide-based compound semiconductor layer is made of amorphous layer and the polycrystal layer that combines with described amorphous layer, and wherein the room temperature band gap of boron phosphide-based compound semiconductor layer is 3.0eV to less than 4.2eV;
(2) as (1) described boron phosphide-based compound semiconductor device, wherein the room temperature band gap of polycrystal layer is less than the room temperature band gap of amorphous layer;
(3) as (1) or (2) described boron phosphide-based compound semiconductor device, wherein polycrystal layer is arranged on the amorphous layer;
(4) as any described boron phosphide-based compound semiconductor device in (1) to (3), wherein amorphous layer and polycrystal layer all are the undoped layers that does not specially mix;
(5) as any described boron phosphide-based compound semiconductor device in (1) to (4), wherein provide the III nitride semiconductor layer to combine with the boron phosphide-based compound semiconductor layer;
(6) as (5) described boron phosphide-based compound semiconductor device, wherein the III nitride semiconductor layer comprises by component formula Al αGa βIn γN (wherein 0≤α, beta, gamma≤1, alpha+beta+γ=1) or Al αGa βIn γN δM 1-δThe compound of (0≤α wherein, beta, gamma≤1, alpha+beta+γ=1,0＜δ≤1, and M is the V group element beyond denitrogenating) expression;
(7) as (6) described boron phosphide-based compound semiconductor device, wherein the boron phosphide-based compound semiconductor layer comprises boron phosphide, and the III nitride semiconductor layer comprises gallium nitride;
(8) as any described boron phosphide-based compound semiconductor device in (5) to (7), wherein the boron phosphide-based compound semiconductor layer is a p type conductive layer, the III nitride semiconductor layer is a n type conductive layer, and the boron phosphide-based compound semiconductor layer combines with the III nitride semiconductor layer to constitute the pn junction structure; And
(9) as any described boron phosphide-based compound semiconductor device in (1) to (8), wherein provide ohmic contact or valve electrode to combine with the boron phosphide-based compound semiconductor layer.
Wherein amorphous fraction and the partially mixed layer of monocrystalline represented in the term of Shi Yonging " polycrystal layer " in the present invention, and perhaps expression comprises the layer of the set of a plurality of cylindricality monocrystalline that crystal orientation is different.
For example, can determine the band gap of boron phosphide-based compound semiconductor layer from the photon energy of imaginary part according to the complex dielectric permittivity that is expressed as 2nk, wherein n is a refractive index, and k is the extinction coefficient of identical wavelength.
In addition, term " polycrystal layer is arranged on the amorphous layer " expression after forming amorphous layer, utilizes amorphous layer to form polycrystal layer as bottom.
The present invention also comprises:
(10) a kind of method of making boron phosphide-based compound semiconductor device, described method is to be used for making as (1) method to (4) any described boron phosphide-based compound semiconductor device, said method comprising the steps of: vapor phase growth amorphous layer under 250 to 1200 ℃ temperature, and under 750 to 1200 ℃ temperature the vapor phase growth polycrystal layer;
(11) as (10) the described method that is used to make boron phosphide-based compound semiconductor device, wherein vapor phase growth amorphous layer and polycrystal layer under identical temperature, and when the vapor phase growth amorphous layer, the V/III ratio is made as 0.2 to 50, and when the vapor phase growth polycrystal layer, the V/III ratio is made as 100 to 500; And
(12) as (10) or (11) the described method that is used to make boron phosphide-based compound semiconductor device, wherein the vapor phase growth speed of amorphous layer is 50 to 80nm/ minutes, and the vapor phase growth speed of polycrystal layer is 20 to 40nm/ minutes.
In the present invention, " V/III than " expression supply to the vapor phase growth zone as the concentration of the V group atom of phosphorus and ratio as the concentration of the III family atom of boron.
In addition, the present invention includes:
(13) a kind of light-emitting diode that comprises laminated construction, described laminated construction obtains by stacking gradually down coating, luminescent layer and overlying strata, wherein luminescent layer is the III nitride semiconductor layer, overlying strata is the boron phosphide-based compound semiconductor layer, described boron phosphide-based compound semiconductor layer comprises amorphous layer and the polycrystal layer that combines with amorphous layer, and has 3.0eV to the room temperature band gap less than 4.2eV.
Description of drawings
Fig. 1 shows the cross section structure of the pn knot LED that makes in embodiment according to the present invention.
Embodiment
Describe the present invention below in detail.
Boron phosphide-based compound semiconductor device
Boron phosphide-based compound semiconductor device of the present invention comprises the boron phosphide-based compound semiconductor layer, and the boron phosphide-based compound semiconductor layer comprises amorphous layer and the polycrystal layer that combines with amorphous layer.By using this structure, can provide the boron phosphide-based compound semiconductor device that comprises the boron phosphide-based compound semiconductor layer with broad-band gap, described band gap at room temperature is that 3.0eV is extremely less than 4.2eV.
In the present invention, " boron phosphide-based compound semiconductor " is the III-V compound semiconductor that comprises boron (B) and phosphorus (P) of cubic zinc blende crystal structure, and the example comprises the compound by following component formulate: B αAl βGa γIn 1-alpha-beta-γP 1-δAs δ(0＜α≤1,0≤β＜1,0≤γ＜1,0＜alpha+beta+γ≤1,0≤δ＜1) and B αAl βGa γIn 1-alpha-beta-γP 1-δN δ(0＜α≤1,0≤β＜1,0≤γ＜1,0＜alpha+beta+γ≤1,0≤δ＜1).Its particular instance comprises single boron phosphide (BP) and mixed crystal, and described mixed crystal comprises a plurality of V group elements, for example boron phosphide gallium indium (component formula: B αGa γIn 1-α-γP, wherein 0＜α≤1,0≤γ＜1), boron nitride phosphorus (component formula: BP 1-δN δ, 0≤δ＜1 wherein) and arsenic boron phosphorus (component formula: B αP 1-δAs δ, 0＜α≤1,0≤δ＜1 wherein).Especially, preferred single boron phosphide is because this is the basic structure that constitutes boron phosphide-based compound semiconductor.The boron phosphide that has a broad-band gap when use is during as stock, the boron phosphide-based mixed crystal that can obtain to have broad-band gap.
The boron phosphide-based compound semiconductor layer can form like this, and by using crystalline substrates as bottom, described substrate is silicon (Si) crystal, sapphire (α-Al for example 2O 3Monocrystalline), hexagonal or cubic silicon carbide (SiC) or gallium nitride (GaN); Perhaps utilize the III nitride semiconductor layer or the analog that on described crystalline substrates, form.
Preferably form the boron phosphide-based compound semiconductor layer by method of vapor-phase growing, described method is for example: the halogen method is (referring to Nippon Kessho Seicho Gakkai Shi (Journal of JapaneseAssociation of Crystal Growth), Vol.24, No.2, page 150 (1997)), the halide method (referring to, J.Crystal Growth, 24/25, pp.193-196 (1974)), molecular beam epitaxial method (referring to, J.Solid State Chem., 133, pp.269-272 (1997)), and metal organic chemical vapor deposition (MOCVD) method (referring to, Inst.Phys.Conf.Ser., No.129, pp.157-162, IOP Publishing Ltd., UK (1993)).Wherein, preferred MOCVD method is because use for example boron triethyl ((C of the easy material that decomposes 2H 5) 3B) as the boron source, thus vapor phase growth amorphous layer at a lower temperature.
In the present invention, do not limit formation and constitute the amorphous layer of boron phosphide-based compound semiconductor layer and the order of polycrystal layer, yet, for example exist in the situation of Macrolattice mismatch between crystalline substrates and the boron phosphide compound semiconductor at the material that constitutes bottom, be preferably formed amorphous layer, on amorphous layer, form polycrystal layer then and combine, because the amorphous layer of boron phosphide-based compound semiconductor has the function that alleviates lattice mismatch with amorphous layer, thereby, can obtain not have the polycrystal layer in crack.
Polycrystal layer is being arranged under the situation of amorphous layer, the thickness of amorphous layer is preferably 2nm or more.If the thickness of amorphous layer is less than 2nm, then amorphous layer can not growth equably on the whole surface of bottom, with the surface of even covering bottom of deposited amorphous layer on it.In boron phosphide-based compound semiconductor device of the present invention, when the thickness of amorphous layer was bigger, the band gap of boron phosphide-based compound semiconductor layer was advantageously wideer.For example, when the thickness of amorphous layer was 50nm, the room temperature band gap of boron phosphide-based compound semiconductor layer was about 4.2eV.
The thickness of amorphous layer or polycrystal layer can actually be measured like this, by utilizing high resolution scanning electron microscope (SEM) or the transmission electron microscope (TEM) of for example measuring thickness.
In boron phosphide-based compound semiconductor of the present invention, preferably provide the III nitride semiconductor layer to combine with the boron phosphide-based compound semiconductor layer.The example of III group-III nitride semiconductor comprises by component formula Al αGa βIn γThe compound of N (wherein 0≤α, beta, gamma≤1, alpha+beta+γ=1) expression, gallium nitride for example, and by component formula Al αGa βIn γN δM 1-δThe compound of (0≤α wherein, beta, gamma≤1, alpha+beta+γ=1,0＜δ≤1, and M is the V group element beyond denitrogenating) expression.
Under the situation of for example boron phosphide-based compound semiconductor of single boron phosphide (BP), be different from the III group-III nitride semiconductor, can obtain the low-resistance p type conductive layer of primary (as-grown) state easily.On the other hand, under the situation of III group-III nitride semiconductor, vapor phase growth n type conductive layer easily.Therefore, when providing n type III nitride semiconductor layer to combine, can easily constitute pn heterojunction structure with suitable barrier height difference with p type boron phosphide-based compound semiconductor layer.For example, can utilize such luminescent layer to constitute and have the luminous component of barrier height difference for the pn heterojunction structure of about 0.3eV, described luminescent layer comprises the n type indium gallium nitride (Ga of room temperature band gap for about 2.7eV βIn γN, wherein 0≤beta, gamma≤1) and band gap be the p type boron phosphide layer of about 3.0eV.This pn junction structure with broad-band gap boron phosphide layer goes for constituting the pn junction diode with high-breakdown-voltage.
Especially, when the boron phosphide-based compound semiconductor layer comprises boron phosphide, and the III nitride semiconductor layer can form the boron phosphide-based compound semiconductor layer with excellent quality when comprising gallium nitride (GaN), and this is preferred.
A shaft lattice constant with boron phosphide (BP) of cubic zinc blende crystal structure is 0.454nm, thereby, boron phosphide { spacing of lattice on the 111} crystal face is 0.319nm.On the other hand, a shaft lattice constant with gallium nitride (GaN) of wurtzite crystal structure is 0.318nm.And a shaft lattice constant of cube gallium nitride is 0.451nm.Like this, boron phosphide { spacing of lattice on the 111} crystal face is basic consistent with a shaft lattice constant of Wurzite structure or cube gallium nitride.Because this almost do not have a lattice mismatch, the high-quality crystallization boron phosphide layer that the defect concentrations in crystals of misfit dislocation for example of can growing on hexagonal or cube gallium nitride single crystal layer reduces.Thereby, can be from boron phosphide layer and hexagonal or cube gallium nitride layer, formation can prevent to produce the heterojunction structure of partial breakdown, and it goes for LED, LD etc.
When the boron phosphide-based compound semiconductor layer that will specially mix when for example the bottom of III nitride semiconductor layer combines, the impurity in the boron phosphide-based compound semiconductor layer spreads sometimes or invades bottom, thereby has reduced the electrical property of bottom.For example, on the III nitride semiconductor layer that comprises n type gallium nitride single crystal, form boron phosphide layer, described boron phosphide layer becomes p type conductive layer by adding magnesium (Mg), the magnesium that is added diffuses into n type gallium nitride single crystal layer, thereby electronic compensating n type charge carrier, as a result, gallium nitride layer becomes high resistant.
Therefore, in the present invention, preferably constitute amorphous layer and polycrystal layer by the so-called undoped layer that does not specially mix, it constitutes the boron phosphide-based compound semiconductor layer.When constituting the boron phosphide-based compound semiconductor layer by undoped layer, can obtain such pn junction structure, described structure can influence the bottom that combines with it sharply, and for example the III nitride semiconductor layer is preferred like this.
By controlling vapor phase growth temperature etc., can form unadulterated p type boron phosphide-based compound semiconductor layer.For example, when on (0.0.0.1.) surface at gallium nitride single crystal during vapor phase growth unadulterated (111) boron phosphide, obtain p type conductive layer under about 1000 ℃ vapor phase growth temperature easily surpassing, and under about 1000 ℃ or following temperature, obtain n type conductive layer easily.
Under the situation of boron phosphide-based compound semiconductor, even dopant states not, also can obtain carrier concentration is 1 * 10 19Cm -3Or higher low-resistance p type or n type conductive layer.For example, can obtain such p type conductive layer, its carrier concentration at room temperature is about 2 * 10 19Cm -3, and have low-resistance value, for example its resistivity (resistance coefficient) is about 5 * 10 -2Ω cm.Especially, under surpassing 1000 ℃ high temperature, during the vapor phase growth amorphous layer, can obtain the lower boron phosphide-based compound semiconductor layer of overall resistance effectively.On this low-resistance p type or n type boron phosphide-based compound semiconductor layer, can advantageously generate excellent contact Ohmic electrode (Ohm contact electrode) or valve electrode.
Described ohmic electrode material can be to be for general on the material that forms Ohmic electrode on the III-V compound semiconductor layer, for example GaAs (GaAs).For example, on p type boron phosphide layer, can form the p type Ohmic electrode that comprises billon (for example gold (Au) zinc (Zn), gold (Au) beryllium (Be)), and on n type boron phosphide layer, can form the n type Ohmic electrode that comprises billon (for example gold (Au) germanium (Ge), gold (Au) tin (Sn), gold (Au) indium (In)).
When on the boron phosphide-based compound semiconductor layer, forming the Ohmic electrode of contact property excellence, for example, can obtain to have low forward voltage (V f) or low threshold voltage (V Th) LED or LD, this is preferred.Especially preferably form Ohmic electrode on such boron phosphide-based compound semiconductor layer, described semiconductor layer is constructed like this, and is below amorphous layer is arranged on, that polycrystal layer is disposed thereon.This is because at room temperature, polycrystal layer has littler band gap than amorphous layer, thereby obtains to have the Ohmic electrode of excellent contact property easily.For example, can use such structure to make high electron mobility MESFET suitably, in described structure, the polycrystal layer that source electrode or drain electrode Ohmic electrode setting and band gap is littler contacts.
As mentioned above, preferably below amorphous layer is arranged on, that polycrystal layer is disposed thereon, constitute the boron phosphide-based compound semiconductor layer, but also can adopt the structure of counter-rotating.By polycrystal layer is set, the bigger amorphous layer of band gap is set then thereon, the boron phosphide-based compound semiconductor layer that is constituted is applicable to and forms non-valve electrode (for example Schottky contact electrode).Schottky contact electrode material can be the material that is often used in forming on the III-V compound semiconductor layer Schottky contact electrode, for example aluminium (Al), gold (Au), titanium (Ti), tantalum (Ta) and niobium (Nb).
Such structure is suitable for forming for example field-effect transistor (MESFET), in described structure, the Schottky contact electrode is set on the high resistant amorphous layer, and the polycrystal layer that will be arranged under the amorphous layer is used as electron supply layer.
Be used to form the method for boron phosphide-based compound semiconductor layer
Describe the method that is used to form the boron phosphide-based compound semiconductor layer of the present invention below in detail, described semiconductor layer constitutes boron phosphide-based compound semiconductor device.
By utilizing different epitaxially growing equipments or identical epitaxially growing equipment, can form amorphous layer and polycrystal layer, it constitutes the boron phosphide-based compound semiconductor layer.Yet, consider from the productivity ratio aspect, preferably by utilizing these layers of the continuous vapor phase growth of identical epitaxially growing equipment.
For example, by utilizing identical epitaxially growing equipment, can be to form amorphous layer under the temperature in 250 to 1200 ℃ of scopes, vapor phase growth polycrystal layer under 750 to 1200 ℃ temperature then.The order that forms amorphous layer and polycrystal layer can be put upside down.When forming amorphous layer, the vapor phase growth temperature is suitably for 250 ℃ or higher, thereby constitutes the source material thermal decomposition fully of the element of amorphous layer, thereby forms described layer.On the other hand, when forming polycrystal layer, the vapor phase growth temperature is suitably for 750 ℃ or higher, thereby quickens crystallization.When formation was two-layer, the vapor phase growth temperature was suitably for 1200 ℃ or lower, thereby can suppress form for example B 13P 2The situation of polyhedron boron under, form the boron phosphide-based compound semiconductor that comprises the boron phosphide-based compound semiconductor layer of single boron phosphide (BP) or utilize boron phosphide.
By utilizing identical epitaxially growing equipment, can also be under identical temperature vapor phase growth amorphous layer and polycrystal layer continuously.In this case, the supply of the source material of the element of formation boron phosphide-based compound semiconductor can change continuously or progressively than (V/III ratio).By changing the V/III ratio, can differentially form amorphous layer and polycrystal layer.For example, from boron chloride (BCl 3) and phosphorus trichloride (PCl 3) in the halogen method of vapor-phase growing of beginning, can supply to the PCl in vapor phase growth zone by control 3Flow velocity and BCl 3Velocity ratio, regulate the V/III ratio.
Forming amorphous layer and forming thereon then under the situation of polycrystal layer, its can by lower V/III than under form amorphous layer and then than above-mentioned high V/III than under the vapor phase growth polycrystal layer realize.On the contrary, forming polycrystal layer and forming thereon then under the situation of amorphous layer, its can by with V/III than realizing to low from hypermutation.And, when the V/III ratio periodically changes, can alternately, periodically form amorphous layer and polycrystal layer.The V/III ratio that is suitable for the vapor phase growth amorphous layer is 0.2 to 50, and the V/III ratio that is suitable for forming polycrystal layer is 100 to 500.
For example, by x x ray diffraction method or electron beam diffraction method, the layer that can identify formation from the diffraction pattern that obtains is amorphous layer or polycrystal layer.
Vapor phase growth speed for amorphous layer and polycrystal layer does not have specific limited, but when the speed of growth of amorphous layer during greater than the speed of growth of polycrystal layer, can advantageously generate the boron phosphide-based compound semiconductor layer that integral body has broad-band gap.Especially, preferably with 50 to 80nm/ minutes speed growth amorphous layer, with 20 to 40nm/ minutes speed growth polycrystal layer of the speed that is lower than the vapor phase growth amorphous layer.
Can mainly constitute for example quantity delivered of the unit interval of boron of element, the speed of growth when being adjusted in vapor phase growth amorphous layer and polycrystal layer by the III family that supplies to the vapor phase growth zone.Yet in the vapor phase growth under surpassing 1000 ℃ temperature, the speed of growth may be according to the concentration in the phosphorus source in the vapor phase growth zone and fluctuation.Therefore, for the speed of growth of the vapor phase growth under the meticulous adjusting high temperature, the III family that preferred accurately adjusting supplies to the vapor phase growth zone constitutes the amount of element and V family formation element.
For example, by utilizing boron triethyl ((C 2H 5) 3B)/hydrogen phosphide (PH 3)/H 2In the MOCVD method vapor phase growth boron phosphide amorphous layer of reaction system, the amount when the boron source of supplying with is set to about 2.5 * 10 -4Rub/minute, the amount in the phosphorus source supplied with is set to about 5.1 * 10 -3Rub/minute the time, under 1025 ℃, can obtain about 60nm/ minute the speed of growth.
In the present invention, constitute the boron phosphide-based compound semiconductor layer by amorphous layer and the polycrystal layer that combines with amorphous layer, therefore, as mentioned above, such boron phosphide-based compound semiconductor device can be provided, it comprises the boron phosphide-based compound semiconductor layer, and described semiconductor layer has broad-band gap, and for example the room temperature band gap is extremely less than 4.2eV from 3.0eV.In the present invention, the amorphous layer that constitutes the boron phosphide-based compound semiconductor layer has been brought into play main effect, makes boron phosphide-based compound semiconductor have large band gap.
The boron phosphide-based compound semiconductor device of the boron phosphide-based compound semiconductor layer of broad-band gap that comprises of the present invention goes for LED, LD etc., and it has the bigger heterojunction structure of barrier height difference, and has excellent device performance.For example, have broad-band gap for example the room temperature band gap to be 3.0eV can be applicable to coating etc. to the boron phosphide-based compound semiconductor layer less than 4.2eV in LED or LD, described coating has the barrier potential difference above 0.3eV, it is even as big as limiting the charge carrier in the luminescent layer.And in LED, the boron phosphide-based compound semiconductor layer goes for Window layer, and by it, the black light of emission or short-wavelength visible light can be penetrated into the outside as needed.
Below by reference example the present invention is described.
(example)
For boron phosphide-based compound semiconductor device of the present invention, made light-emitting diode (LED) with pn double heterojunction (DH) structure, described structure comprises the boron phosphide-based compound semiconductor layer, and described semiconductor layer is made of the amorphous layer and the polycrystal layer of vapor phase growth on the Si single crystalline substrate.The exemplary cross section structure that shows the LED of manufacturing of Fig. 1.
For substrate 101, use n type (111) the Si single crystalline substrate of Doping Phosphorus (P).
At first, by atmospheric pressure (approximate atmospheric pressure) metal organic vapor (MOVPE) method, deposition boron phosphide (BP) amorphous layer 102 that do not mix on (111) surface of substrate 101.By utilizing boron triethyl ((C 2H 5) 3B) as the boron source, utilize hydrogen phosphide (PH 3) as the phosphorus source, 450 ℃ of deposit boron phosphide amorphous layer 102.To offer the ratio (PH of the concentration in the concentration in phosphorus source of MOVPE reaction system and boron source the unit interval 3/ (C 2H 5) 3The V/III ratio) is set to 16.The thickness of boron phosphide amorphous layer 102 is 10nm.
Stop to supply with the boron source to finish vapor phase growth boron phosphide amorphous layer 102.Then, at phosphorus source (PH 3) and hydrogen (H 2) mist in the temperature of substrate 101 is elevated to 925 ℃.Subsequently, flow into the boron source again, and under 925 ℃, on boron phosphide amorphous layer 102, deposit not Doped n-type { 111} boron phosphide single crystalline layer 103.In vapor phase growth, the V/III ratio is made as 1300.The thickness of boron phosphide single crystalline layer 103 is 120nm.
On the boron phosphide single crystalline layer, by utilizing gallium (Ga)/ammonia (NH 3)/hydrogen (H 2) the hydride VPE method of reaction system, comprise the following coating 104 of gallium nitride (GaN) monocrystalline 1050 ℃ of deposit.Described coating layer ranges in thickness down is 3 μ m.
On following coating 104, by utilizing trimethyl gallium ((CH 3) 3Ga)/trimethyl indium ((CH 3) 3In)/H 2The atmospheric pressure MOCVD method of reaction system comprises n type indium gallium nitride (Ga 850 ℃ of following vapor phase growths 0.90In 0.10N) n type luminescent layer 105.The carrier concentration of n type luminescent layer 105 is 7 * 10 17Cm -3, and bed thickness is 50nm.
On n type luminescent layer 105, by utilizing (C 2H 5) 3B/PH 3/ H 2The atmospheric pressure MOCVD method of reaction system is at 1025 ℃ of following vapor phase growth boron phosphide amorphous layer 106a.When vapor phase growth boron phosphide amorphous layer 106a with V/III than (=PH 3/ (C 2H 5) 3B) be made as 16, and with 50nm/ minute speed growth boron phosphide amorphous layer 106a.Vapor phase growth is accurately continued 30 seconds, is the boron phosphide amorphous layer 106a of 25nm to form thickness.Immediately, the increase supply PH in vapor phase growth zone 3Flow velocity, so that the V/III ratio is increased to 120, thus deposition boron phosphide polycrystal layer 106b on boron phosphide amorphous layer 106a subsequently.Speed of growth vapor phase growth boron phosphide polycrystal layer 106b with 30nm/ minute.The thickness of boron phosphide polycrystal layer is 380nm.By like this, formed such p type boron phosphide layer 106, its thickness is 405nm, and comprises the double-decker of do not mix the boron phosphide amorphous layer 106a and the boron phosphide polycrystal layer 106b that do not mix.
Measure by conventional Hall effect, the carrier concentration of measuring the p type boron phosphide layer 106 of acquisition is about 1 * 10 19Cm -3
In addition, the room temperature band gap of determining the p type boron phosphide layer 106 of acquisition from photon energy is about 3.6eV, the extinction coefficient (k) that described photon energy is measured based on refractive index (n) with by conventional ellipsometer long-pending (=2nk), thereby find, p type boron phosphide layer 106 goes for the overlying strata of luminescent layer 105, can also be used as Window layer,, be penetrated into the outside as needed from the emission of luminescent layer 105 by described Window layer.
The dislocation density of the p type boron phosphide layer 106 that measure to obtain by conventional cross section TEM method, and measure on average less than 1 * 10 3/ cm 2Dislocation density is 1 * 10 2/ cm 2Or also part existence of littler zone.
Core at the p type boron phosphide layer 106 that is used as overlying strata provides the p type Ohmic electrode 107 with sandwich construction, and described structure comprises AuBe alloy (Au99 quality %Be1 quality %) lower floor and Au upper strata.Also has the circle that diameter is about 120 μ m with the p type Ohmic electrode 107 of wire bonds as pad electrode.On the other hand, the n type Ohmic electrode 108 that comprises aluminium (Al) antimony (Sb) alloy is set on the almost whole back side of substrate 101.
By like this, made LED with pn double heterojunction (DH) structure, wherein n type luminescent layer 105 is clipped in the following coating 104 that comprises n type gallium nitride layer and comprises between the overlying strata of p type boron phosphide layer 106.
The operating current of the 20mA of logical forward between the p type of the LED that obtains and n type Ohmic electrode 107 and 108, the result launches the blue zone light of wavelength for about 430nm.By utilizing the brightness of conventional integrating sphere measured chip attitude, and measure and be 7mcd.In addition, find that by near field emission figure emissive porwer is uniform on the almost whole surface of luminescent layer 105.This is because Ohmic electrode 107 is set to contact with the p type boron phosphide layer 106 of low-dislocation-density.And therefore, suppressed in routine techniques, because device operation current is by the generation of the low-light point of the short circuit current generation of dislocation.
The band gap that calculates luminescent layer 105 from emission wavelength is about 2.9eV, and reaches about 0.7eV with the difference of the band gap of the p type boron phosphide layer 106 of formation overlying strata.In addition, because Ohmic electrode 107 is set to contact with the p type boron phosphide layer 106 with low-dislocation-density, thereby partial breakdown does not take place.Therefore, provide the LED of rectification characteristic excellence, wherein under the forward current of 20mA, forward voltage (V f) be about 3V, under the reverse current of 10 μ A, reverse voltage (V r) be 8V or bigger.
As mentioned above, in this example, provide such LED, it not only has excellent rectification characteristics, also has uniform luminous intensity.
Industrial usability
According to the present invention, consisted of boron phosphide-basedization by amorphous layer and the polycrystal layer of being combined with amorphous layer Compound semiconductor layers, thus the boron phosphide-based compound semiconductor device of device performance excellence can be provided, Described device comprises the boron phosphide-based compound semiconductor layer of broad-band gap, and its room temperature band gap is that 3.0eV arrives Less than 4.2eV.

Claims (13)

1. boron phosphide-based compound semiconductor device comprises:
Luminescent layer; And
The overlying strata that constitutes by the boron phosphide-based compound semiconductor layer that on described luminescent layer, provides, described boron phosphide-based compound semiconductor layer is made of amorphous layer and the polycrystal layer that combines with described amorphous layer,
The room temperature band gap of wherein said boron phosphide-based compound semiconductor layer is that 3.0eV is extremely less than 4.2eV.
2. boron phosphide-based compound semiconductor device as claimed in claim 1, the room temperature band gap of wherein said polycrystal layer is less than the room temperature band gap of described amorphous layer.
3. boron phosphide-based compound semiconductor device as claimed in claim 1, wherein said amorphous layer forms on described luminescent layer.
4. boron phosphide-based compound semiconductor device as claimed in claim 1, wherein said amorphous layer and described polycrystal layer all are the undoped layers that does not specially mix.
5. boron phosphide-based compound semiconductor device as claimed in claim 1 wherein provides the described luminescent layer that is made of the III nitride semiconductor layer to combine with the described overlying strata that is made of described boron phosphide-based compound semiconductor layer.
6. boron phosphide-based compound semiconductor device as claimed in claim 5, wherein said III nitride semiconductor layer comprises by component formula Al as described luminescent layer αGa βIn γN or Al αGa βIn γN δM 1-δThe compound of expression, 0≤α wherein, beta, gamma≤1, alpha+beta+γ=1,0＜δ≤1, and M is the V group element beyond denitrogenating.
7. boron phosphide-based compound semiconductor device as claimed in claim 6, wherein said boron phosphide-based compound semiconductor layer comprises boron phosphide as described overlying strata, and described III nitride semiconductor layer comprises gallium nitride as described luminescent layer.
8. boron phosphide-based compound semiconductor device as claimed in claim 5, wherein said boron phosphide-based compound semiconductor layer is a p type conductive layer as described overlying strata, described III nitride semiconductor layer is a n type conductive layer as described luminescent layer, and described boron phosphide-based compound semiconductor layer combines with described III nitride semiconductor layer to constitute the pn junction structure.
9. boron phosphide-based compound semiconductor device as claimed in claim 1 wherein provides ohmic contact or valve electrode to combine with described boron phosphide-based compound semiconductor layer.
10. method of making boron phosphide-based compound semiconductor device, described method is the method that is used to make boron phosphide-based compound semiconductor device as claimed in claim 1, said method comprising the steps of: vapor phase growth amorphous layer under 250 to 1200 ℃ temperature, and under 750 to 1200 ℃ temperature the vapor phase growth polycrystal layer.
11. the method that is used to make boron phosphide-based compound semiconductor device as claimed in claim 10, wherein described amorphous layer of vapor phase growth and described polycrystal layer under identical temperature, and when the described amorphous layer of vapor phase growth, the V/III ratio is made as 0.2 to 50, and when the described polycrystal layer of vapor phase growth, described V/III ratio is made as 100 to 500.
12. the method that is used to make boron phosphide-based compound semiconductor device as claimed in claim 10, the vapor phase growth speed of wherein said amorphous layer are 50 to 80nm/ minutes, and the vapor phase growth speed of described polycrystal layer is 20 to 40nm/ minutes.
13. light-emitting diode that comprises laminated construction, described laminated construction obtains by stacking gradually down coating, luminescent layer and overlying strata, wherein said luminescent layer is the III nitride semiconductor layer, described overlying strata is the boron phosphide-based compound semiconductor layer, described boron phosphide-based compound semiconductor layer comprises amorphous layer and the polycrystal layer that combines with described amorphous layer, and has 3.0eV to the room temperature band gap less than 4.2eV.
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US5005057A (en) * 1989-04-28 1991-04-02 Kabushiki Kaisha Toshiba Semiconductor light-emitting diode and method of manufacturing the same
US5241553A (en) * 1991-01-10 1993-08-31 Fujitsu Limited Laser diode for producing an optical beam at a visible wavelength
US6069021A (en) * 1997-05-14 2000-05-30 Showa Denko K.K. Method of growing group III nitride semiconductor crystal layer and semiconductor device incorporating group III nitride semiconductor crystal layer

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US5005057A (en) * 1989-04-28 1991-04-02 Kabushiki Kaisha Toshiba Semiconductor light-emitting diode and method of manufacturing the same
US5241553A (en) * 1991-01-10 1993-08-31 Fujitsu Limited Laser diode for producing an optical beam at a visible wavelength
US6069021A (en) * 1997-05-14 2000-05-30 Showa Denko K.K. Method of growing group III nitride semiconductor crystal layer and semiconductor device incorporating group III nitride semiconductor crystal layer

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