CN100552994C - Nitride semiconductor photogenerator and manufacture method thereof - Google Patents
Nitride semiconductor photogenerator and manufacture method thereof Download PDFInfo
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Abstract
The invention provides a kind of nitride semiconductor photogenerator, it comprises positive electrode and the negative electrode with high adhesion, can output high-power, and do not produce heat; Particularly, the invention provides a kind of nitride semiconductor photogenerator, it comprises ohmic contact layer at least, p type nitride semiconductor layer, nitride semiconductor light-emitting layer and the n type nitride semiconductor layer that is layered on the plating layer, wherein between described ohmic contact layer and described plating layer, form the plating adhesion coating, and described plating adhesion coating by comprise 50 quality % or bigger be included in described plating layer in the alloy of the identical composition of the main component of alloy constitute.
Description
Technical field
The present invention relates to a kind of nitride semiconductor photogenerator and manufacture method thereof, particularly, relate to a kind of nitride semiconductor photogenerator and manufacture method thereof that comprises plating layer, wherein this plating layer fully supports lamination after at the bottom of the peeling liner.
The cross reference of related application
According to 35U.S.C. § 119 (e), the application requires in the U.S. Provisional Application No.60/718 of submission on September 21st, 2005,738 rights and interests, and require Japanese patent application No.2005-312819 that submits in the Japanese patent application No.2005-265300 that submitted on September 13rd, 2005, on October 27th, 2005 and the U.S. Provisional Application No.60/718 that submitted on September 21st, 2005,738 priority is incorporated herein its content as a reference.
Background technology
In recent years, as the semi-conducting material that is used for the short-wave long light-emitting device, the GaN compound semiconductor materials has received a lot of concerns.By mocvd method (MOCVD method) or molecular beam epitaxial method (MBE method), the GaN compound semiconductor is formed on oxide substrate for example on sapphire single-crystal substrate or the III-V compounds of group substrate.
The sapphire single-crystal substrate has lattice constant with GaN and differs by more than and equal 10% lattice constant.Yet,, therefore be extensive use of the sapphire single-crystal substrate owing to can form nitride-based semiconductor by on the sapphire single-crystal substrate, forming the resilient coating that comprises AlN or AlGaN with good characteristic.For example, as shown in Figure 5, when using sapphire single-crystal substrate 1, n type GaN semiconductor layer 3, GaN luminescent layer 4 and p type GaN semiconductor layer 5 order according to this are formed on the sapphire single-crystal substrate 1.Because sapphire single-crystal substrate 1 is an insulator, usually, in the device 20 that comprises sapphire single-crystal substrate 1, be formed on negative electrode 12 on the n type GaN semiconductor layer 3 and the positive electrode 13 that is formed on the p type GaN semiconductor layer 5 and be positioned on the side of device 20, shown in Figure 4 and 5.Be used for comprising the method for facing up and Flipchip method from the example that the device 20 that is included in the negative electrodes on the side extracts the method for light, wherein in the method for facing up, use transparency electrode for example ITO as positive electrode, extract light from the p semiconductor side, and in Flipchip method, use highly reflective film for example Ag extracts light as positive electrode from sapphire substrate side.
As mentioned above, the sapphire single-crystal substrate is widely used.Yet because sapphire is an insulator, the sapphire single-crystal substrate has some problems.At first, in order to form negative electrode 12, expose n N-type semiconductor N 3 by etching luminescent layer 4, as shown in Figure 5, therefore, the area of luminescent layer 4 has reduced the area of negative electrode 12, and power output reduces.The second, because positive electrode 13 and negative electrode 12 are positioned on the same side, levels of current flows, and current density increases partly, and device 20 is heated.The 3rd, because the thermal conductivity of Sapphire Substrate 1 is low, the hot indiffusion that is produced, thus the temperature of device 20 raises.
In order to address these problems, use such method, wherein electrically-conductive backing plate is attached to and comprises and stacking gradually on the device of the n type semiconductor layer on the sapphire single-crystal substrate, luminescent layer and p type semiconductor layer, remove the sapphire single-crystal substrate, positive electrode and negative electrode (for example, the open No.3511970 of Japan Patent (mandate)) are set on two surfaces of the lamination that is produced then.
In addition, by plating rather than by attached, form electrically-conductive backing plate (for example, the patent application of Japanese unexamined discloses 2001-274507 for the first time).
In addition, when forming electrically-conductive backing plate by plating, forming the intermediate layer, is adherence (adhesion) (for example, the patent application of Japanese unexamined for the first time openly 2004-47704) between p N-type semiconductor N and the electrically-conductive backing plate to improve between p N-type semiconductor N and the plating layer.
Summary of the invention
The example that is used for the method for attached electrically-conductive backing plate comprise wherein will have low-melting metallic compound for example AuSn as the method for adhesive and the activation knot method that wherein under vacuum, activates the surface that will engage by argon plasma.These methods require will be attached surface flat-satin extremely.Therefore, if there is for example particle of foreign matter on surface that will be attached, this zone just can not be by closely attached.Owing to this reason, be difficult to obtain uniform surfaces for attachment.
Obtaining under the situation of electrically-conductive backing plate on the p type semiconductor layer by plating, this method is subjected to the several adverse effects from foreign matter.Yet in order to form the film of making by plating as electrically-conductive backing plate, must make its thickness is 10 μ m or bigger, thereby has problems when being attached to p type conductive layer.
Usually, in order closely contacting forming between electrically-conductive backing plate and the p type semiconductor layer, on the p conductive layer, to be formed for the ohmic contact layer of ohmic contact, and on ohmic contact layer, to form electrically-conductive backing plate by plating.
Patent application in Japanese unexamined discloses among the 2004-47704 for the first time, by forming the intermediate layer as the plating basement membrane between ohmic contact layer and electrically-conductive backing plate (plating layer), has improved adherence.In the patent application of Japanese unexamined for the first time openly among the 2004-47704, in example, disclose a kind of usefulness that constitutes by Au or AuGe that comprises and acted on the device in intermediate layer of the plating basement membrane of Ni plating.Yet these plating basement membranes that are used for plating can not be realized enough adherences.
As the result who concentrates on the effort research that addresses these problems, the inventor finds, by comprising the type of the n at least nitride semiconductor layer that stacks gradually, the nitride semiconductor light-emitting layer, p type nitride semiconductor layer, the nitride semiconductor photogenerator of ohmic contact layer and plating layer, wherein between ohmic contact layer and plating layer, form plating adhesion coating (plate adhesion layer), and the plating adhesion coating by comprise 50 quality % or bigger be included in plating layer in the alloy of the identical composition of the main component of alloy constitute, obtain between ohmic contact layer and plating layer, to have high adhesion and do not cause the nitride semiconductor photogenerator of peeling off.Just, the invention provides following nitride semiconductor photogenerator and manufacture method thereof.
(1) a kind of nitride semiconductor photogenerator, comprise the ohmic contact layer at least, p type nitride semiconductor layer, nitride semiconductor light-emitting layer and the n type nitride semiconductor layer that are layered on the plating layer, wherein between described ohmic contact layer and described plating layer, form the plating adhesion coating, and described plating adhesion coating by comprise 50 quality % or bigger be included in described plating layer in the alloy of the identical composition of the main component of alloy constitute.
(2) according to the nitride semiconductor photogenerator of (1), the thickness of wherein said plating layer is in the scope of 10 μ m to 200 μ m.
(3) according to the nitride semiconductor photogenerator of (3), wherein said plating layer is made of the NiP alloy.
(4) according to the nitride semiconductor photogenerator of (4), wherein said plating layer is made of Cu or Cu alloy.
(5) according to the nitride semiconductor photogenerator of (3), wherein said plating adhesion coating is made of the NiP alloy.
(6) according to the nitride semiconductor photogenerator of (4), wherein said plating adhesion coating is made of Cu or Cu alloy.
(7) according to the nitride semiconductor photogenerator of (1) or (2), the thickness of wherein said plating adhesion coating is in the scope of 0.1nm to 2 μ m.
(8) according to the nitride semiconductor photogenerator of (1) or (2), wherein said ohmic contact layer is made of at least one that is selected from Pt, Ru, Os, Rh, Ir, Pd, Ag and alloy thereof.
(9) according to the nitride semiconductor photogenerator of (1) or (2), the thickness of wherein said ohmic contact layer is in the scope of 0.1nm to 30nm.
(10) according to the nitride semiconductor photogenerator of (1) or (2), wherein on described ohmic contact layer, form the reflector that constitutes by Ag or Ag alloy.
(11) a kind of method of making nitride semiconductor photogenerator may further comprise the steps: make at least resilient coating, n type nitride semiconductor layer, nitride semiconductor light-emitting layer, p type nitride semiconductor layer, ohmic contact layer, plating adhesion coating and plating layer according to this sequential cascade on the substrate that constitutes by oxide monocrystal or semiconductor monocrystal; Remove described substrate and described resilient coating then; And form electrode then.
(12) method of the manufacturing nitride semiconductor photogenerator of basis (11) wherein forms described plating adhesion coating by sputtering method.
(13) method of the manufacturing nitride semiconductor photogenerator of basis (11) or (12) wherein forms described plating layer by electroless deposition process.
(14) method of the manufacturing nitride semiconductor photogenerator of basis (11) or (12) wherein forms described plating layer by the electrolysis method for plating.
(15) method of the manufacturing nitride semiconductor photogenerator of basis (11) or (12) wherein after forming described plating layer, heats the product that is obtained in scope under 100 ℃ to 300 ℃ temperature.
Description of drawings
Fig. 1 illustrates the cross section structure of nitride semiconductor photogenerator of the present invention.
Fig. 2 illustrates the cross section of the lamination that comprises the substrate that is used to form nitride semiconductor photogenerator of the present invention and plating layer.
Fig. 3 illustrates the cross section of the lamination that comprises plating layer that obtains by the lamination that comprises substrate and plating layer shown in the manuscript 2.
Fig. 4 is the plan view that an example of conventional nitride semiconductor photogenerator is shown.
Fig. 5 is the cross sectional view along the line A-A ' intercepting of Fig. 4.
Embodiment
Embodiments of the invention will be described with reference to the accompanying drawings.Yet, the invention is not restricted to following examples, for example, can be the combination of following examples.
Fig. 1 illustrates the cross section structure of nitride semiconductor photogenerator of the present invention.
Nitride semiconductor photogenerator 10 of the present invention comprises plating layer 9.On the surface of plating layer 9, stack gradually plating adhesion coating 8, reflector 7, ohmic contact layer 6, p type nitride semiconductor layer 5, nitride semiconductor light-emitting layer 4 and n type nitride semiconductor layer 3, wherein reflector 7 is for having the Ag film of 30nm thickness, ohmic contact layer 6 is used as contact layer for Pt film, the p type nitride semiconductor layer 5 with 1.5nm thickness and for having the Mg doped p type GaN layer of 150nm thickness, n type nitride semiconductor layer 3 is as contact layer and for having the Si doped n type GaN layer of 5 μ m thickness.On n type nitride semiconductor layer 3, form negative electrode 12 by transparency electrode 11.On another surface of plating layer 9, form positive electrode 13.
Nitride semiconductor light-emitting layer 4 comprise according to this that order is provided with lower floor: the n type In with 30nm thickness
0.1Ga
0.9N coating (clad layer); By stacked Si GaN barrier layer that mixes and In with 2.5nm thickness
0.2Ga
0.8N trap layer five times and further at In
0.2Ga
0.8The GaN barrier layer that stacked Si mixes on the N trap layer and the multi-quantum pit structure that obtains; And Mg doped p type Al
0.07Ga
0.93The N coating.
Form ohmic contact layer 6 that constitutes by Pt and the reflector 7 that constitutes by Ag by sputtering method.Be formed for the figure of Pt and Ag by conventional photoetching and lift-off technology.
Fig. 2 illustrates the cross section of the lamination that comprises the substrate that is used to form nitride semiconductor photogenerator 10 of the present invention and plating layer.The lamination that comprises substrate and plating layer comprises the substrate 1 that is made of sapphire, and n type nitride semiconductor layer 3, nitride semiconductor light-emitting layer 4, p type nitride semiconductor layer 5, ohmic contact layer 6, reflector 7, plating adhesion coating 8 and plating layer 9 are formed on the substrate 1 by resilient coating 2.After making the lamination that comprises substrate and plating layer, remove substrate 1 and resilient coating 2 by polishing, to make the lamination that comprises plating layer 102 shown in Fig. 3 with this structure.Then, by on two surfaces of the lamination 102 that comprises plating layer, forming electrode, make nitride semiconductor photogenerator 10 with the structure shown in Fig. 1.
The example of material that is used to make the substrate 1 of the lamination 101 that comprises substrate and plating layer comprises for example sapphire single-crystal (Al of oxide monocrystal
2O
3A face, C face, M face and R face), spinelle monocrystalline (MgAl
2O
4), ZnO monocrystalline, LiAlO
2Monocrystalline, LiGaO
2Monocrystalline and MgO monocrystalline; And conventional backing material for example Si monocrystalline, SiC monocrystalline and GaAs monocrystalline.These materials can be used for substrate 1 and without any restriction.When the substrate that conductive substrates for example is made of SiC is used as substrate 1, when on being manufactured on two surface, comprising the luminescent device of positive electrode and negative electrode, needn't remove substrate.Yet, owing to the resilient coating of insulation can not be used, and the crystal deterioration of the nitride semiconductor layer of on resilient coating, growing, therefore can not make luminescent device with good characteristic.Therefore, in the present invention, even when being used for substrate 1, also be necessary to remove substrate at SiC that will conduction or Si.
Form resilient coating 102, to alleviate because the stress effect that the mismatch of the lattice constant between substrate 1 and the n type nitride semiconductor layer 3 causes.For example, when forming the crystal layer that is made of GaN on the substrate 1 that is being made of sapphire single-crystal, the lattice constant of sapphire single-crystal and the lattice constant of GaN differ 10% or bigger.In order to improve the crystallinity of GaN, for example AlN and AlGaN are used for resilient coating 2 with the material of its lattice constant between the lattice constant of sapphire single-crystal and GaN.In the present invention, certainly with AlN and AlGaN as resilient coating 2 and without any restriction.
On resilient coating 102, form semiconductor light emitting structure.The lamination that comprises substrate and plating layer 101 shown in Fig. 2 comprises nitride-based semiconductor, particularly, comprises n type nitride semiconductor layer 3, nitride semiconductor light-emitting layer 4 and p type nitride semiconductor layer 5.Can for example double-heterostructure (DH), quantum well structure or multi-quantum pit structure be used for the present invention with the ray structure of any routine.
As nitride-based semiconductor, known by general molecular formula Al
xIn
yGa
1-x-yMany semiconductors of N (0≤x＜1,0≤y＜1, and x+y＜1) expression.In the present invention, can use the nitride-based semiconductor represented by this general molecular formula and without any restriction.
Do not limit and be used for these process for producing nitride semiconductor.The present invention can use known conduct be used to grow all methods of method of III group-III nitride semiconductor, for example mocvd method (MOCVD), hydride gas-phase epitaxy (HVPE) or molecular beam epitaxial method (MBE).Wherein, from the viewpoint of film thickness controllability and mass productivity, MOCVD is preferred.
When using MOCVD to make nitride-based semiconductor, preferably with hydrogen (H
2) or nitrogen (N
2) as carrier gas; With trimethyl gallium (TMG) or triethyl-gallium (TEG) Ga source as III clan source material; Trimethyl aluminium (TMA) or triethyl aluminum (TEA) are used as the Al source; Trimethyl indium (TMI) or triethylindium (TEI) are used as the In source; And with ammonia (NH
3) or hydrazine (N
2H
4) as the N source of group V source material.As n type dopant, for example, preferably with monosilane (SiH
4) or disilane (Si
2H
6) as the Si source, and preferably with germane (GeH
4) as the Ge source.As p type dopant, for example, preferably with bis-cyclopentadienyl magnesium (Cp
2Mg) or two ethyl cyclopentadienyl group magnesium ((EtCp)
2Mg) as the Mg source.
In order stably to obtain low contact resistance, the thickness of ohmic contact layer 6 is preferably 0.1nm or bigger, more preferably 1nm or bigger.Especially, when the thickness of ohmic contact layer 6 is 1nm or when bigger, can obtain uniform contact resistance.
On ohmic contact layer 6, form the reflector 7 that constitutes by Ag, Al or its alloy.As seen to ultraviolet wavelength, Ag and Al have the reflectivity higher than Pt, Ir, Rh, Ru, Os and Pd.Just, owing to reflected effectively, use the reflector that constitutes by Ag, Al or its alloy can make high-power device from the light of nitride semiconductor light-emitting layer 4.In addition, when reflector 7 is made of Ag, Al or its alloy and makes ohmic contact layer 6 enough thin when allowing light to pass, except obtaining good ohmic contact, also can obtain enough reverberation.Therefore, can make high-power device.The thickness of ohmic contact layer 6 is preferably 30nm or littler, more preferably 10nm or littler.When ohmic contact layer 6 had thickness in this preferable range, enough reverberation passed ohmic contact layer 6.
Do not limit the manufacture method that is used for ohmic contact layer 6 and reflector 7, the example of its manufacture method comprises conventional sputter and deposition process.
On ohmic contact layer 6, form plating layer 9 by plating adhesion coating 8.
In order to obtain good adherence, the thickness of plating adhesion coating 8 is preferably 0.1nm or bigger, more preferably 1nm or bigger.When the thickness with plating adhesion coating 8 is adjusted into 0.1nm or when bigger, can obtains uniform adherence.Though the thickness to plating adhesion coating 8 does not have the upper limit, from the viewpoint of productivity ratio, it is preferably 2 μ m or littler.
Do not limit the manufacture method that is used for plating adhesion coating 8 especially, the example comprises conventional sputtering method and deposition process.Owing in sputtering method, have high-octane sputter particles bombardment substrate surface to form film, can form film with high adhesion.Therefore, preferably sputtering method is used to form plating adhesion coating 8.After formation has the plating adhesion coating 8 of high adhesion as mentioned above, form plating layer 9 with big thickness.
Because plating layer 9 is the support base that are used to support the major part of luminescent device 10, therefore be necessary to have the thickness and the intensity of the major part that is enough to support luminescent device 10.Just, plating layer 9 is the plating substrates that are used to support ray structure.
Electroless plating and electrolysis plating can be used to make plating layer 9.When using electroless plating, preferably use the NiP alloy.When using the electrolysis method for plating, preferably use Cu or Cu alloy.
In order to keep the sufficient intensity that is used for support base, the thickness of plating layer 9 is preferably 10 μ m or bigger.If plating layer 9 is blocked up, then plating layer 9 is peeled off and the productivity ratio reduction easily; Therefore, preferred thickness is 200 μ m or littler.
Before plating, preferably use widely used neutral detergent degreasing and clean the surface of plating adhesion coating 8.In addition, the also preferred for example surface of nitric acid chemical etching plating adhesion coating 8 of acid of using is to remove the natural oxide film on plating adhesion coating 8.
When plating layer 9 was NiP coating, the preferred use comprised nickel source for example nickelous sulfate and nickel chloride and for example plating bath (plating bath) of hypophosphites of phosphorus source, forms plating layer 9 by electroless plating.The example that is used for the commercially produced product that is fit to that the plating of electroless plating bathes comprises by Uemura﹠amp; Co., Ltd sells
HDX.Preferably in 4 to 10 scope, its temperature is preferably in 30 to 95 ℃ scope for the pH that bathes at the plating during the electroless plating.
When plating layer 9 was Cu or Cu alloy layer, the preferred use comprised for example plating bath of copper sulphate of Cu source, forms plating layer 9 by the electrolysis plating.Plating bath during the electrolysis plating is preferably highly acid, and just, its pH is preferably 2 or littler.Its temperature preferably in 10 to 50 ℃ scope, room temperature (25 ℃) more preferably.Current density preferably 0.5 to 10A/dm
2Scope in, more preferably 2 to 4A/dm
2Scope in.In addition, in order to make smooth surface, preferably leveler (leveling agent) is added to plating and bathe.The example of the commercially produced product of employed leveler comprises by Uemura﹠amp; Co., the ETN-1-A and the ETN-1-B of Ltd sale.
In order to improve the adherence of plating layer 9 and plating adhesion coating 8, preferred heat treatment plating layer 9.Heat treatment temperature is preferably in 100 to 300 ℃ scope, to improve adherence.If heat treatment temperature is higher than 300 ℃, then adherence further improves, but ohm property can deterioration.
After forming plating layer 9, Sapphire Substrate 1 is removed with resilient coating 2, to produce the lamination that comprises plating layer 102 shown in Fig. 3.The example of the removal method of substrate 1 comprises any conventional method, for example polishing, etching or laser lift-off.
After having removed substrate 1, resilient coating 2 by polishing, etching etc., n type nitride-based semiconductor 3 exposes, as shown in Figure 3.
After this, on n type nitride semiconductor layer 3, form negative electrode 12.As negative electrode 12, known negative electrode with various The Nomenclature Composition and Structure of Complexes.In the present invention, can be without any restrictedly using conventional negative electrode.For example, for the whole surface to n type nitride semiconductor layer 3 applies voltage, form transparency electrode 11, for example ITO forms the negative electrode 12 that comprises Cr, Ti and Au layer, as shown in Figure 1 then.
As the positive electrode 13 that is formed on the plating layer 9, the known various positive electrodes that comprise Au, Al, Ni, Cu etc.In the present invention, can be without any restrictedly using conventional positive electrode.
Like this, make nitride semiconductor photogenerator, it comprises positive electrode and the negative electrode with high adhesion, exportable high power, and do not produce heat.
Example
Below, reference example and comparative example are illustrated preferred embodiment according to nitride semiconductor photogenerator of the present invention.
Example 1
On Sapphire Substrate, stacking gradually by thickness is that resilient coating, the thickness that the AlN of 10nm constitutes is the Si doped n type GaN contact layer of 5 μ m, the n type In that thickness is 30 μ m
0.1Ga
0.9The N coating.Then, stacked luminescent layer on coating with many well structures, Si doped n type GaN barrier layer and thickness that wherein stacked five thickness are 30nm are the In of 2.5nm
0.2Ga
0.8N trap layer, stacked then barrier layer.After this, the Mg doped p type Al that continuous stacked thickness is 50nm on luminescent layer
0.07Ga
0.93N coating and thickness are the Mg doped p type GaN contact layer of 150nm.
Forming thickness on the p type contact layer of the nitride-based semiconductor that produces by sputtering at then, is the Pt layer of 1.5nm.After this, formation thickness is the Ag layer of 30nm on the Pt layer by sputtering at.Form Pt and Ag figure by conventional photoetching and lift-off technology.
Then, by sputter form the NiP alloy film that thickness is 30nm (Ni:80at%, P:20at%), to produce the plating adhesion coating.
Under 25 ℃, salpeter solution (5N) was immersed 30 seconds in the surface of NiP alloy film, to remove the oxidation film that on the surface of NiP alloy film, forms.
Then, use plating to bathe (by Uemura﹠amp; Co., Ltd sells
HDX-7G), forming by thickness on the NiP alloy film is the electroless plating film that the NiP alloy of 50 μ m constitutes, to produce plating layer (metal-plated substrate).Carry out electroless plating under such condition, wherein pH is 4.6, and temperature is 90 ℃, and the processing time is 3 hours.After water cleaning and the dry lamination that comprises substrate and plating layer that is produced, use the cleaning stove under 250 ℃, it to be heated 1 hour.
After this, remove Sapphire Substrate and resilient coating, to expose the n type semiconductor layer by polishing.
On the n type semiconductor layer, forming thickness by deposition is the ITO film (SnO of 400nm
2: 10 quality %).Then, the surface by being deposited on ITO in form in the heart and comprise that thickness is that the Cr film of 40nm, Ti film and the thickness that thickness is 100nm are 1, the negative electrode of the Au film of 000nm.Form the figure of negative electrode by conventional photoetching and lift-off technology.
On the surface of p type semiconductor layer, comprise that thickness is 1, the positive electrode of the Au film of 000nm by deposition formation.
Then, by section the lamination that is produced is divided into nitride semiconductor photogenerator shown in Figure 1.
In order to estimate adherence, after forming and heating comprises the lamination of substrate and plating layer, peel off test.As peel off test, the accelerated test method that the method that use is stipulated combines with the thermal shock method in JIS H8602-1992.Just, use cutter in ohmic contact layer and plating layer, to form the wire cut, have 1mm grid at interval so that produce.The degree of depth of cut is adjusted into the distance on the surface that reaches Sapphire Substrate.Then, after under 200 ℃, in stove, heating 30 minutes, in water, make lamination be cooled fast to 20 ℃, make its drying then.After this, with adhesive tape (by NichibanCo., the adhesive tape that Ltd. sells, width: 12mm) tight adhesion is to the surface of the plating layer that wherein forms the wire cut, then from the sur-face peeling adhesive tape of plating layer.Then, to not counting from the quantity that forms the residual subregion that 100 subregions being of a size of 1mm * 1mm peel off by the wire cut.Just, when 100 branch block reservations, it is be evaluated as " not peeling off ".The results are shown in the table 1.
Example 2 and 3 and comparative example 1 to 3
Except the composition and thickness that change plating adhesion coating and plating layer, to prepare with the identical mode of example 1 and to estimate nitride semiconductor photogenerator.Evaluation result is shown in Table 1.
Example 4
Except form thickness by sputtering method is that the Cu film of 30nm substitutes the NiP alloy film as the plating adhesion coating and is that the Cu film of 50 μ m substitutes the NiP alloy film as plating layer with electrolysis method for plating formation thickness, to prepare with the identical mode of example 1 and to estimate nitride semiconductor photogenerator.Evaluation result is shown in Table 1.
In addition, electrolysis plating Cu wherein uses the CuSO that comprises 80g/L to produce plating layer under such condition
4, the sulfuric acid of 200g/L and leveler be (by Uemura﹠amp; Co., Ltd sells, the ETN-1-A of 1.0mL/L and the ETN-1-B of 1.0mL/L) plating bathe, current density is 2.5A/cm
2, the plating time is 3 hours, and the material that will comprise cupric phosphate is as anode.
Comparative example 4 to 6
The plating adhesion coating that has composition shown in the table 1 and thickness except formation substitutes the plating adhesion coating that is made of Cu, to prepare and to estimate the nitride semiconductor photogenerator of comparison with the identical mode of example 4.Evaluation result is shown in Table 1.
Table 1
By table 1 clearly, the nitride semiconductor photogenerator of example 1 to 3 has good plating adhesion coating and the adherence between the plating layer, wherein in the nitride semiconductor photogenerator of example 1 to 3, plating layer is made of NiP by electroless plating, and the plating adhesion coating also is made of the NiP with the plating layer identical materials.Comparatively speaking, by table 1 clearly, do not have in the comparative example 1 in the nitride semiconductor photogenerator that comprises the plating adhesion coating that constitutes by the Au that does not comprise NiP in the nitride semiconductor photogenerator, comparative example 2 of plating adhesion coating and the comparative example 3 and comprise that the nitride semiconductor photogenerator of the plating adhesion coating that is made of the AuGe that does not comprise NiP is very poor aspect adherence yet.
In addition, by table 1 clearly, the nitride semiconductor photogenerator of example 4 has good plating adhesion coating and the adherence between the plating layer, wherein in the nitride semiconductor photogenerator of example 4, plating layer is made of Cu by the electrolysis plating, and the plating adhesion coating also is made of Cu.Comparatively speaking, by table 1 clearly, do not have in the comparative example 4 in the nitride semiconductor photogenerator that comprises the plating adhesion coating that constitutes by the Au that does not comprise Cu in the nitride semiconductor photogenerator, comparative example 5 of plating adhesion coating and the comparative example 6 and comprise that the nitride semiconductor photogenerator of the plating adhesion coating that is made of the AuGe that does not comprise Cu is very poor aspect adherence yet.
Industrial usability
Nitride semiconductor photogenerator of the present invention is such nitride semiconductor photogenerator, its Have higher adherence and do not peel off, and it is by shape between Ohmic contact layer and plating layer Become plating adhesion layer and by comprising 50 quality % or bigger and the master who is included in the alloy in the plating layer The alloy of wanting the identical composition of composition forms plating adhesion layer and produces. As a result, the invention provides one Kind have comprise on the surface thereon of high-quality and stability and the lower surface positive electrode and negative electrode Optical device.
In addition, the plating layer of one of assembly of nitride semiconductor photogenerator of the present invention has is enough to The thickness of the main assembly of supporting device and intensity. Therefore, plating layer can be steady during manufacture process Surely supporting device.
Claims (15)
1. a nitride semiconductor photogenerator comprises the ohmic contact layer at least, p type nitride semiconductor layer, nitride semiconductor light-emitting layer and the n type nitride semiconductor layer that are layered on the plating layer,
Wherein between described ohmic contact layer and described plating layer, form the plating adhesion coating, and
Described plating adhesion coating by comprise 50 quality % or bigger be included in described plating layer in the alloy of the identical composition of the main component of alloy constitute.
2. according to the nitride semiconductor photogenerator of claim 1, the thickness of wherein said plating layer is in the scope of 10 μ m to 200 μ m.
3. according to the nitride semiconductor photogenerator of claim 1 or 2, wherein said plating layer is made of the NiP alloy.
4. according to the nitride semiconductor photogenerator of claim 1 or 2, wherein said plating layer is made of Cu or Cu alloy.
5. according to the nitride semiconductor photogenerator of claim 3, wherein said plating adhesion coating is made of the NiP alloy.
6. according to the nitride semiconductor photogenerator of claim 4, wherein said plating adhesion coating is made of Cu or Cu alloy.
7. according to the nitride semiconductor photogenerator of claim 1 or 2, the thickness of wherein said plating adhesion coating is in the scope of 0.1nm to 2 μ m.
8. according to the nitride semiconductor photogenerator of claim 1 or 2, wherein said ohmic contact layer is made of at least one that is selected from Pt, Ru, Os, Rh, Ir, Pd, Ag and alloy thereof.
9. according to the nitride semiconductor photogenerator of claim 1 or 2, the thickness of wherein said ohmic contact layer is in the scope of 0.1nm to 30nm.
10. according to the nitride semiconductor photogenerator of claim 1 or 2, wherein on described ohmic contact layer, form the reflector that constitutes by Ag, Al or its alloy.
11. a method of making nitride semiconductor photogenerator may further comprise the steps:
Make at least resilient coating, n type nitride semiconductor layer, nitride semiconductor light-emitting layer, p type nitride semiconductor layer, ohmic contact layer, plating adhesion coating and plating layer according to this sequential cascade on the substrate that constitutes by oxide monocrystal or semiconductor monocrystal;
After this, remove described substrate and described resilient coating; And
Form electrode then.
12. the method according to the manufacturing nitride semiconductor photogenerator of claim 11 wherein forms described plating adhesion coating by sputtering method.
13. the method according to the manufacturing nitride semiconductor photogenerator of claim 11 or 12 wherein forms described plating layer by electroless deposition process.
14. the method according to the manufacturing nitride semiconductor photogenerator of claim 11 or 12 wherein forms described plating layer by the electrolysis method for plating.
15., wherein after forming described plating layer, under 100 ℃ to 300 ℃ temperature, heat the product that is obtained in scope according to the method for the manufacturing nitride semiconductor photogenerator of claim 11 or 12.
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| JP4107868B2 (en) * | 2002-04-16 | 2008-06-25 | シャープ株式会社 | Method for manufacturing nitride-based semiconductor light-emitting device |
| JP3896044B2 (en) * | 2002-07-11 | 2007-03-22 | シャープ株式会社 | Nitride-based semiconductor light-emitting device manufacturing method and product |
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| JP2005203519A (en) * | 2004-01-14 | 2005-07-28 | Sumitomo Electric Ind Ltd | Semiconductor light emitting device |
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