CN101506946A - Method for manufacturing group III nitride compound semiconductor light-emitting device, group III nitride compound semiconductor light-emitting device, and lamp - Google Patents

Method for manufacturing group III nitride compound semiconductor light-emitting device, group III nitride compound semiconductor light-emitting device, and lamp Download PDF

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CN101506946A
CN101506946A CNA200780030345XA CN200780030345A CN101506946A CN 101506946 A CN101506946 A CN 101506946A CN A200780030345X A CNA200780030345X A CN A200780030345XA CN 200780030345 A CN200780030345 A CN 200780030345A CN 101506946 A CN101506946 A CN 101506946A
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iii
compound semiconductor
nitride compound
emitting device
iii nitride
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CN101506946B (en
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三木久幸
塙健三
佐佐木保正
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Toyoda Gosei Co Ltd
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Showa Denko KK
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Priority claimed from JP2006291082A external-priority patent/JP2008106316A/en
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Priority claimed from PCT/JP2007/065902 external-priority patent/WO2008020599A1/en
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    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
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    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
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    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
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    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
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    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
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    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
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    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
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    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
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Abstract

Disclosed is a method for manufacturing a group III nitride compound semiconductor light-emitting device having excellent emission characteristics at high yield. Also disclosed are a group III nitride compound semiconductor light-emitting device and a lamp.Specifically disclosed is a method for manufacturing a group III nitride compound semiconductor light-emitting device, which comprises a step wherein a semiconductor layer composed of a group III nitride compound semiconductor containing Ga as a group III element is formed on a substrate (11) by sputtering. In this method, the substrate (11) and a sputtering target are arranged opposite to each other, and the distance between the substrate (11) and the sputtering target is set within the range of 20-100 mm. In addition, when the semiconductor layer is formed by sputtering, the bias value applied to the substrate (11) is set at 0.1 W/cm<2> or higher. Furthermore, when the semiconductor layer is formed, the sputtering is performed while supplying nitrogen and argon into a chamber which is used for the sputtering.

Description

The manufacture method of III group-III nitride compound semiconductor light-emitting device, III group-III nitride compound semiconductor light-emitting device and lamp
Technical field
The present invention relates to be applicable to the manufacture method of the III group-III nitride compound semiconductor light-emitting device of light-emitting diode (LED), laser diode (LD), electronic device etc., particularly relate to and to make the good III group-III nitride compound semiconductor crystallization of crystallinity on substrate, carry out manufacture method, III group-III nitride compound semiconductor light-emitting device and the lamp of epitaxially grown III group-III nitride compound semiconductor light-emitting device.
The application based on August 18th, 2006 spy in Japanese publication be willing to 2006-223260 number and special be willing to 2006-223261 number and on October 26th, 2006 spy in Japanese publication be willing to require priority 2006-291082 number, its content is quoted in the application.
Background technology
III family (the 3rd main group) nitride semiconductor luminescent element has and is equivalent to by the band gap of visible light to the Direct Transfer type of the energy of the scope of ultraviolet region, the luminous efficiency excellence, and the light-emitting component that therefore can be used as LED and LD etc. uses.
In addition, when being used for electronic device, III group-III nitride semiconductor light-emitting component is compared during with the III-V compound semiconductor that uses in the past, can obtain having the electronic device of excellent specific property.
Such III group-III nitride compound semiconductor, usually with trimethyl gallium, triethyl-gallium and ammonia as raw material, adopt mocvd method to make.Mocvd method is to make the steam that contains raw material in the carrier gas and be transported to substrate surface, by decomposing with the reaction of heated substrate, thereby makes the method for crystalline growth.
In the past, as the single-crystal wafer of III-V compound semiconductor, on the single-crystal wafer of different materials, made crystalline growth and the method that obtains is common.Like this, at the variety classes substrate with carry out between the crystallization of epitaxially grown III group-III nitride semiconductor, there is bigger lattice unconformity (mismatch) thereon.For example, at sapphire (Al 2O 3) when making gallium nitride (GaN) growth on the substrate, there is 16% lattice unconformity between the two, when making the gallium nitride growth on the SiC substrate, between is deposited 6% lattice unconformity.
Usually, when above-mentioned such big lattice unconformity exists, be difficult on substrate, make crystallization directly to carry out epitaxial growth, in addition, even there is the problem that can not obtain the good crystallization of crystallinity when growing.
Therefore following scheme was once proposed, promptly, utilize Metalorganic Chemical Vapor Deposition (MOCVD), when on sapphire single crystal substrate or SiC monocrystal substrate, making the crystallization of III group-III nitride semiconductor carry out epitaxial growth, the at first stacked layer that is called low temperature buffer layer that forms by aluminium nitride (AlN) or AlGaN on substrate, at high temperature make the crystallization of III group-III nitride semiconductor carry out epitaxially grown method more thereon, this scheme is carried out (for example patent documentation 1,2) usually.
On the other hand, also studied by sputter and made the crystallization of III group-III nitride compound semiconductor, for example once proposed following scheme, that is, and by using the high frequency magnetron sputtering of nitrogen, at (100) face and the Al of Si 2O 3(0001) face on form the method (for example non-patent literature 1) of GaN film.In the method that non-patent literature 1 is put down in writing, as the condition of film forming, making total gas pressure is that 2mTorr, input electric power are 100W, and substrate temperature ℃ is changed in RT～900, in addition, as sputter equipment, makes the device of target and substrate subtend.
In addition, once proposed following scheme, that is, make negative electrode relative, and between substrate and target, be added with the method (for example non-patent literature 2) of the device formation GaN film of screen cloth with target.In the method that non-patent literature 2 is put down in writing, as membrance casting condition, in nitrogen, making pressure is 0.67Pa, and making substrate temperature is 84～600 ℃, and input electric power is 150W, and the distance between substrate and the target is 80mm.
In addition, once proposed following scheme,, on substrate, formed the method (for example non-patent literature 3) of AlN film by making the target mode that is called faces cathode respect to one another.
In addition, once propose use DC magnetron sputtering method, on substrate, formed the method (for example non-patent literature 4) of AlN film.In the method that patent documentation 4 is put down in writing, make substrate and target subtend, at Ar and N 2Mixed-gas atmosphere in carry out sputter, as membrance casting condition, pressure is changed between 60～180mm in the distance of scope, substrate and the target of 0.2～0.8Pa.
In addition, following scheme was once proposed, this scheme relates to by layers such as the formation of the method beyond MOCVD AlN as resilient coating, adopt mocvd method to be formed on the method for the layer of institute's film forming on the resilient coating again, for example passing through on the resilient coating of high-frequency sputtering film forming, adopt the method (for example, patent documentation 3) of the crystallization of mocvd method growth phase composition together.But in the method that patent documentation 3 is put down in writing, existence can not stably obtain the problem (with reference to patent documentation 4,5) of good crystallization.
Therefore,, once proposed following scheme, for example, comprising the method (for example, patent documentation 4) of annealing in the mist of ammonia and hydrogen after the buffer growth in order stably to obtain good crystallization; With the method (for example, patent documentation 5) that under the temperature more than 400 ℃, forms resilient coating by the DC sputter.
In addition, in patent documentation 4 and 5 methods of being put down in writing, as baseplate material, can use sapphire, silicon, carborundum, zinc oxide, gallium phosphide, GaAs, magnesium oxide, manganese oxide, III group-III nitride based compound semiconductor monocrystalline etc., wherein preferred sapphire a face substrate.
Patent documentation 1: No. 3026087 communique of Japan Patent
Patent documentation 2: Japanese kokai publication hei 4-297023 communique
Patent documentation 3: the special fair 5-86646 communique of Japan
Patent documentation 4: No. 3440873 communique of Japan Patent
Patent documentation 5: No. 3700492 communique of Japan Patent
Non-patent literature 1: ox nine BUGY CRAXONE (Y.USHIKU) etc., " 21 century associating Conference Papers collection ", Vol.2nd, p295 (2003)
Non-patent literature 2: テ イ-キ Network マ (T.Kikuma) etc., " vacuum (Vacuum) ", Vol.66, P233 (2002)
Non-patent literature 3: キ Network オ ト ミ Na ガ (Kikuo Tominaga) etc., " Japanese applicating physical magazine (Japanese Journal of Applied Physics) ", Vol.28, p7 (1989)
Non-patent literature 4: エ system イ シ Ha ラ (M.Ishihara) etc., " thin solid film (ThinSolid Films) ", Vol.316, p152 (1998)
Summary of the invention
But, the applicant etc. carry out found that of deep experiment, research, even when carrying out film forming, can not stably obtain containing the III group-III nitride compound semiconductor of Ga as III family element with good crystallization according to the condition of record in patent documentation 4 and the patent documentation 5.That is, in patent documentation 4,5 methods of being put down in writing, on the resilient coating that adopts sputtering film-forming, adopt mocvd method to form the GaN layer.When adopting sputtering method to form resilient coating, film forming speed is fast, but according to membrance casting condition, becomes the resilient coating of crystallinity difference sometimes.When on the low resilient coating of such crystallinity, when adopting mocvd method to make the GaN layer growth, worry that the crystallinity of GaN layer significantly reduces.
In addition, use the condition of non-patent literature 1,2 records, when adopting sputtering method to form the GaN layer, also have the problem that is difficult on resilient coating, form the good GaN layer of crystallinity.
The present invention finishes in view of above-mentioned problem, its purpose is to provide can stablize and form with the short time crystalline film that is formed by III group-III nitride compound semiconductor have good uniformity, in the time of the productivity ratio excellence, have manufacture method, III group-III nitride compound semiconductor light-emitting device and the lamp of the III group-III nitride compound semiconductor light-emitting device of the excellent characteristics of luminescence.
The result that the inventor furthers investigate in order to address the above problem has finished the present invention.That is, the present invention relates to following scheme.
[1] a kind of manufacture method of III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, in with described substrate and the configuration of sputtering target subtend ground, make the scope that is spaced apart 20～100mm of described substrate and described sputtering target.
[2] a kind of manufacture method of III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when forming described semiconductor layer, the power that puts on sputtering target applies by high-frequency mode or pulsed D C mode.
[3] a kind of manufacture method of III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when forming described semiconductor layer, making the indoor vacuum degree of using in sputter in advance is 1.0 * 10 -3After Pa is following, to described indoor base feed.
[4] a kind of manufacture method of III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that making the pass, position of described substrate and sputtering target is in the face of formula.
[5] a kind of manufacture method of III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when forming described semiconductor layer, make the magnetic field rotation or make magnetic field shake (swing) with respect to sputtering target.
[6] manufacture method of each described III group-III nitride compound semiconductor light-emitting device of basis [1]～[5] is characterized in that, forms described semiconductor layer by the reactive sputtering method that the nitride raw material is circulated in reactor.
[7] according to the manufacture method of [6] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that, use nitrogen as described nitride raw material.
[8] manufacture method of each described III group-III nitride compound semiconductor light-emitting device of basis [1]～[7] is characterized in that, forms the resilient coating that comprises column crystallization between described substrate and described semiconductor layer.
[9] according to the manufacture method of [8] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that, adopt sputtering method to form described resilient coating.
[10] according to the manufacture method of [8] or [9] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that, form described resilient coating by the III group-III nitride compound that contains as the Al of III family element.
[11] according to the manufacture method of [10] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that, form described resilient coating by AlN.
[12] according to the manufacture method of each described III group-III nitride compound semiconductor light-emitting device of [8]～[11], it is characterized in that, form described resilient coating in the mode more than at least 90% on the surface that covers described substrate.
[13] manufacture method of each described III group-III nitride compound semiconductor light-emitting device of basis [8]～[12] is characterized in that the width that constitutes the column crystallization of described resilient coating is the scope of 0.1～100nm.
[14] manufacture method of each described III group-III nitride compound semiconductor light-emitting device of basis [8]～[13] is characterized in that the thickness of described resilient coating is the scope of 10～500nm.
[15] manufacture method of each described III group-III nitride compound semiconductor light-emitting device of basis [8]～[14], it is characterized in that, when forming described resilient coating, form the described semiconductor layer that forms by III group-III nitride compound by GaN by AlN.
[16] manufacture method of each described III group-III nitride compound semiconductor light-emitting device of basis [1]～[15] is characterized in that, described substrate uses sapphire.
[17] a kind of III group-III nitride compound semiconductor light-emitting device, it is to adopt each described manufacture method of above-mentioned [1]～[16] to obtain.
[18] a kind of lamp, it has used above-mentioned 17 described III group-III nitride compound semiconductor light-emitting devices.
[19] a kind of manufacture method of III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when adopting sputtering method to form described semiconductor layer, make bias voltage (bias) value that puts on described substrate be 0.1W/cm 2More than.
[20] a kind of manufacture method of III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when adopting sputtering method to form described semiconductor layer, making the power that puts on sputtering target is 0.1W/cm 2～100W/cm 2Scope.
[21] according to the manufacture method of [19] or [20] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that, form described semiconductor layer in reactor by the reactive sputtering method that the nitride raw material is circulated.
[22] according to the manufacture method of [21] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that, used nitrogen as described nitride raw material.
[23] manufacture method of each described III group-III nitride compound semiconductor light-emitting device of basis [19]～[22] is characterized in that, forms the resilient coating that comprises column crystallization between described substrate and described semiconductor layer.
[24] according to the manufacture method of [23] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that, adopt sputtering method to form described resilient coating.
[25] according to the manufacture method of [24] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that, form described resilient coating by the III group-III nitride compound that contains Al.
[26] according to the manufacture method of [25] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that, form described resilient coating by AlN.
[27] according to the manufacture method of each described III group-III nitride compound semiconductor light-emitting device of [23]～[26], it is characterized in that, form described resilient coating in the mode more than at least 90% on the surface that covers described substrate.
[28] manufacture method of each described III group-III nitride compound semiconductor light-emitting device of basis [23]～[27] is characterized in that the width that constitutes the column crystallization of described resilient coating is the scope of 0.1～100nm.
[29] manufacture method of each described III group-III nitride compound semiconductor light-emitting device of basis [23]～[28] is characterized in that the thickness of described resilient coating is the scope of 10～500nm.
[30] manufacture method of each described III group-III nitride compound semiconductor light-emitting device of basis [23]～[29], it is characterized in that, when forming described resilient coating, form the described semiconductor layer that forms by III group-III nitride compound by GaN by AlN.
[31] manufacture method of each described III group-III nitride compound semiconductor light-emitting device of basis [19]～[30] is characterized in that, described substrate uses sapphire.
[32] a kind of III group-III nitride compound semiconductor light-emitting device, it is to adopt each described manufacture method of above-mentioned [19]～[31] to obtain.
[33] a kind of lamp, it has used above-mentioned [32] described III group-III nitride compound semiconductor light-emitting device.
The invention effect
According to the manufacture method of III group-III nitride compound semiconductor light-emitting device of the present invention,, can adopt sputtering method to form the crystalline film that has good uniformity with the short time by above-mentioned formation.Thus, can stably form the good III group-III nitride compound semiconductor layer of crystallinity.Therefore, can obtain the III group-III nitride compound semiconductor light-emitting device that productivity ratio is excellent and have the excellent characteristics of luminescence.
Description of drawings
Fig. 1 is the figure of an example of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is the skeleton diagram of the cross section structure of expression laminated semiconductor.
Fig. 2 is the figure of an example of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is the skeleton diagram of expression planar structure.
Fig. 3 is the figure of an example of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is the skeleton diagram of expression cross section structure.
Fig. 4 is the lamp that the explanation of pattern ground uses III group-III nitride compound semiconductor light-emitting device of the present invention to constitute.
Fig. 5 is the figure of an example of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is transmission electron microscope (TEM) photo of expression cross section structure.
Fig. 6 is the figure of an example of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is that TEM photo shown in Figure 5 is carried out the figure that medelling is represented.
Fig. 7 is the figure of an example of the manufacture method of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is the skeleton diagram of the structure of the rock type sputter equipment of expression.
Fig. 8 is the figure of an example of the manufacture method of pattern ground explanation III group-III nitride compound semiconductor light-emitting device of the present invention, is the skeleton diagram of the structure of the revolving sputter equipment of expression.
Description of reference numerals
1...III group-III nitride compound semiconductor light-emitting device
10... laminated semiconductor
11... substrate
11a... surface
12... resilient coating
13... basalis
14...n type semiconductor layer
15... luminescent layer
16...p type semiconductor layer
17... light transmission positive pole
3... lamp
Embodiment
(first execution mode)
Below, the execution mode for manufacture method, III group-III nitride compound semiconductor light-emitting device and the lamp of III group-III nitride compound semiconductor light-emitting device of the present invention suitably describes with reference to Fig. 1～7.
The III group-III nitride compound semiconductor light-emitting device of present embodiment (below, sometimes abbreviate light-emitting component as) manufacture method, being to use sputtering method to form the method for the semiconductor layer that is formed by III group-III nitride compound semiconductor on substrate at least, is the method for using the compound that contains Ga as III group-III nitride compound semiconductor.
Use the illustrative laminated semiconductor 10 of Fig. 1, the laminated construction of the light-emitting component that the manufacture method by present embodiment obtains is described.This laminated semiconductor 10 is laminated with the resilient coating 12 that is formed by III group-III nitride compound on substrate 11, on this resilient coating 12, be formed with and stack gradually the semiconductor layer 20 that n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16 form.
Then, the laminated semiconductor 10 of present embodiment, as the example that Fig. 2 and Fig. 3 represent, stacked light transmission positive pole 17 on p type semiconductor layer 16, when forming positive terminal pad 18 more thereon, at the stacked negative pole 19 on the regional 14d that exposes that is formed on the n type contact layer 14b of n type semiconductor layer 14, thereby can constitute light-emitting component 1.
[using the film forming of the semiconductor layer of sputtering method]
The manufacture method of light-emitting component of the present invention, as described above, be to use sputtering method to form the method for the layer of formation semiconductor layer 20 at least on substrate 11, adopt in the present embodiment: the employing sputtering method forms the basalis 14a of the n type semiconductor layer 14 among the formation semiconductor layer 20 and the method for n type contact layer 14b.
In order to use sputtering method on substrate, to form the III group-III nitride compound semiconductor layer of crystallinity excellence, must generate the higher reactive material of energy, make the migration (migration) on the substrate active, be the method for following detailed description in the present embodiment therefore.
As the sputtering method that in the manufacture method of present embodiment, uses, preferably, sputtering target is applied power by using RF (high frequency) sputtering method or DC sputtering method.
In addition, when using reactive sputtering method described later,, more preferably use the RF sputtering method usually from easily controlling the viewpoint of film forming speed.
In addition, in the DC sputtering method, when using the reactive sputtering method, if apply the state of electric field continuously with DC, then sputtering target charging is difficult to improve film forming speed, therefore gives the pulsed DC sputtering method of bias voltage with being preferably pulse feature.
In addition, when adopting sputtering method to form semiconductor layer, carry out the method for film forming by the reactive sputtering method that the nitride raw material is circulated in reactor, can keep crystallinity well by the control reaction, can stably reproduce its good crystallinity, thereby more preferably.
In addition, in the present embodiment, when adopting sputtering method to form semiconductor layer, preferably make the magnetic field rotation or magnetic field is shaken with respect to metallic target 47.
Particularly when using the RF sputter, as the method for avoiding charging, preferred on one side with the position of magnet at target (sputtering target) Yi Bian in the mobile film forming of carrying out.
The movement technique of concrete magnet can suitably be selected according to the kind of sputter equipment, for example, magnet is shaken or rotatablely moves.
In the illustrative sputter equipment 40 of Fig. 7, dispose magnet 42 in the below (below of Fig. 7) of metallic target (sputtering target) 47, this magnet 42, shakes along target platform 43 below metallic target 47 by omitting illustrated drive unit.In chamber 41, supply with nitrogen and argon gas, on the substrate 11 that is installed on heater 44, adopt sputtering method to form semiconductor layer.
In addition, in the illustrative sputter equipment 50 of Fig. 8, below metallic target 47 (below of Fig. 8), dispose oval-shaped magnet 52, this magnet 52 is rotating shaft with the central shaft 53a of the target platform 53 of the circle of having accommodated metallic target 47, is rotated (the arrow R direction of Fig. 8) below metallic target 47.
At this moment, magnet 52, rotation below metallic target 47 under the state of the plasma circle being lived by the magnetic field that utilizes this magnet 52 to produce, so plasma becomes the shape around metallic target 47 surfaces, can have the ground of omission and uses metallic target 47.Therefore in addition, can prevent that metallic target 47 surfaces from being covered by product, have from metal forming 47 to substrate 11, be attached to the effect of substrate 11 efficiently from all directions sputtering particle that disperses.
In the present embodiment, as the important parameters in the film forming of using sputtering method, can enumerate pressure, nitrogen partial pressure, film forming speed, substrate temperature and bias voltage etc. in the stove.
In the manufacture method of present embodiment, when forming semiconductor layer 20, preferably making the chamber 41 interior vacuum degrees of sputter equipment 40 in advance is 1.0 * 10 -3After Pa was following, base feed carried out film forming in chamber 41.
By the vacuum degree in the chamber 41 that makes above-mentioned sputter equipment 40 is above-mentioned scope, becomes low pressure in the chamber 41, becomes the state that has reduced the impurity in the chamber 41.Under this state in chamber 41 base feed, carry out the film forming of semiconductor layer 20, can not sneak into impurity thus, can obtain the good semiconductor layer of crystallinity 20.
Pressure in the chamber 41 when in addition, adopting sputtering method to form semiconductor layer 20 is preferably more than the 0.3Pa.Pressure in the chamber 41 is during less than 0.3Pa, and the amount of nitrogen becomes too small, worries to be attached on the substrate 11 with the state that does not become nitride by the metal of sputter.In addition, the upper pressure limit in the chamber 41 is not particularly limited, but need be suppressed to the pressure of the degree that can produce plasma.
In addition, the nitrogen flow is with respect to nitrogen (N 2) and the ratio of the flow of Ar, preferred N 2It is 20%～98% scope.When being lower than the flow-rate ratio of this scope, splash-proofing sputtering metal is attached on the substrate with metallic state.In addition, when being when being higher than the flow-rate ratio of above-mentioned scope, because the amount of Ar is very few, so sputtering rate is low.
The nitrogen flow is with respect to nitrogen (N 2) and the ratio of the flow of Ar, be preferably 25%～90% scope especially.
In the manufacture method of present embodiment, as described above, make the nitrogen concentration height in the indoor gas of sputter equipment, and then, mix Ar with above-mentioned flow-rate ratio as the big gas of weight.When indoor gas only is nitrogen,, therefore limited film forming speed, in the present embodiment,, when can improving film forming speed, made the migration on the substrate 11 active by mixing with the big Ar of above-mentioned flow-rate ratio and weight owing to knock a little less than the power of metallic target 47.
As the nitrogen raw material that uses in the present embodiment, can be without any restrictedly using known nitrogen compound usually, but ammonia, nitrogen (N2) is because simple to operate and can obtain more cheaply, thus preferred.
The decomposition efficiency of ammonia is good, can carry out film forming with the high speed of growth, but because reactive, toxicity is high, therefore need remove the evil equipment and detector in addition, must make the material of the member that uses in the reaction unit be the high material of chemical stability.
In addition, using nitrogen (N 2) during as raw material, as device can be easy to use device, but can not obtain high reaction speed.But, if,, therefore consider and take into account the nitrogenous source that is best suited for installation cost though then can obtain the film forming speed of the available degree on industrial production of hanging down than ammonia for by importing to the method in the device after the decompose nitrogen such as electric field, heat.
Film forming speed when using the film forming of sputtering method is preferably the scope of second 0.01nm/ second～10nm/.During second, film-forming process is long-time to film forming speed less than 0.01nm/, and waste is big on industrial production.Film forming speed during second, is difficult to obtain good film greater than 10nm/.
In the manufacture method of present embodiment, use sputtering method form to constitute the basalis 14a and the n type contact layer 14b of the n type semiconductor layer 14 among the semiconductor layer 20 at least, therefore film forming speed can be improved, and film forming (manufacturing) time can be shortened.By shortening manufacturing time, can suppress impurity and enter indoor in the sputter equipment to Min..
Substrate 11 preferably carries out the pre-treatment of wet type.For example, for the substrate of being made by silicon 11, carry out RCA washing methods that people know etc., make the surface be the hydrogen terminal, film-forming process is stable thus.
In addition, substrate 11 in importing reactor the back, form before the resilient coating 12, can use the method for sputtering method etc. to carry out pre-treatment.Specifically, can be by substrate 11 be exposed to Ar, N 2Plasma in put the surface in order.For example, by making Ar gas, N 2The action of plasma of gas etc. can be removed the organic substance and the oxide that are attached to substrate 11 surfaces in substrate 11 surfaces.Under this situation, if apply voltage between substrate 11 and chamber, then plasma particle acts on substrate 11 efficiently.
The inventor etc. carry out the result of deep experiment, research, and the temperature of the substrate 11 during film forming is preferably the scope of room temperature～1200 ℃, and more preferably 300 ℃～1000 ℃ scope most preferably is 500 ℃～800 ℃ scope.
The temperature of substrate 11 is prescribed a time limit down less than above-mentioned, has suppressed the migration on the substrate 11, and can not make the good III group-III nitride compound semiconductor crystalline film of crystallinity.The temperature of substrate 11 surpasses above-mentioned going up in limited time, worries III group-III nitride compound semiconductor crystallization decomposition.
In addition, Shuo Ming room temperature in the present invention is the temperature of environment of also having influence on operation etc., but as concrete temperature, is 0～30 ℃ scope.
In the manufacture method of present embodiment, making the temperature of the substrate 11 when adopting sputtering film-forming is above-mentioned scope, and substrate temperature is improved, and the reactive material (from the metal of metallic target 47 taking-ups) that arrives substrate 11 is activated in the motion of crystal surface.
When using sputtering method to form mixed crystal, the method that the metal that becomes target is prepared as the mixture (can form alloy) of metal material is in advance arranged, can also be two targets preparing to constitute by different materials, and the method for side by side carrying out sputter.
For example, when forming the film of definite composition, can use the target of composite material, when different several films is formed in formation, can be arranged at a plurality of targets indoor.
In the manufacture method of present embodiment, in substrate 11 and the configuration of metallic target (sputtering target) 47 subtends ground, the interval of substrate 11 and metallic target 47 is preferably the scope of 20～100mm, the more preferably scope of 30～50mm.
Interval by making substrate 11 and metallic target 47 can be supplied with the reactive material of higher energy to substrate 11 in above-mentioned scope, and the migration on the substrate comes to life, and can form the III group-III nitride compound semiconductor layer of crystallinity excellence.
In the manufacture method of present embodiment, preferably making the pass, position of substrate 11 and metallic target 47 is in the face of formula.
As described above, in the chamber 41 of sputter equipment 40, by becoming substrate 11 is disposed at formation in the plasma, higher energy is supplied to substrate 11, so the migration on the substrate 11 comes to life, and the cyclisation of dislocation is carried out easily.
Thus, can form the III group-III nitride compound semiconductor layer of crystallinity excellence.
In the manufacture method of present embodiment, by under these conditions, at least use sputtering method form to constitute the basalis 14a and the n type contact layer 14b of the n type semiconductor layer 14 among the semiconductor layer 20, can generate high bias voltage or high-power reactive material, in addition, this reactive material can be supplied with to substrate 11 with high kinergety, therefore on substrate 11, be produced migration, make the dislocation cyclisation easily.Thus, constitute the basalis 14a of the n type semiconductor layer 14 of semiconductor layer 20, the crystallinity as the resilient coating 12 of the aggregate of the column crystallization of film forming on substrate 11 is not inherited on former state ground.Therefore, can be formed into membrane efficiency height, productivity ratio excellence, and the III group-III nitride compound semiconductor of crystallinity excellence.
[laminated construction of light-emitting component]
Below describe in detail for the formation of the light-emitting component 1 that obtains by the present embodiment manufacture method of on substrate 11, using sputtering method to form semiconductor layer 20 at least as mentioned above.
＜substrate 〉
In the present embodiment,,, just be not particularly limited, can select various materials to use so long as can make the crystallization of III group-III nitride compound semiconductor carry out epitaxially grown baseplate material on the surface as the material that can be used for substrate 11.For example, can enumerate sapphire, SiC, silicon, zinc oxide, magnesium oxide, manganese oxide, zirconia, manganese oxide zinc-iron, oxidation magnalium, zirconium boride, gallium oxide, indium oxide, lithia gallium, lithia aluminium, neodymia gallium, lanthana strontium aluminium tantalum, strontium oxide strontia titanium, titanium oxide, hafnium, tungsten, molybdenum etc.
In addition, do not use ammonia and form resilient coating, and adopt the method for using ammonia to form the basalis that constitutes n type semiconductor layer described later, and, use is known at high temperature contacting the occasion of oxide substrate that ammonia causes chemical modification, metal substrate etc. in the aforesaid substrate material, the resilient coating of present embodiment plays a role as coating, is being effective aspect the chemical modification that prevents substrate therefore.
In addition, the temperature that common sputtering method can suppress substrate makes it lower, even therefore use the occasion of the substrate of being made by the material with the character of at high temperature decomposing, also can not cause damage to substrate 11, and can carry out the film forming of each layer on substrate.
＜resilient coating 〉
The laminated semiconductor 10 of present embodiment adopts sputtering method to be formed with the resilient coating 12 that is formed by III group-III nitride compound on substrate 11.By sputtering method, for example, by raw metal and the gas that comprises V group element by plasma-activated, react, can form resilient coating 12.
For the laminated semiconductor 10 of the III group-III nitride compound semiconductor light-emitting device 1 of present embodiment, when on substrate 11, making the crystallization of III group-III nitride compound semiconductor carry out epitaxial growth, can be by with III family raw metal with comprise sputtering method that the gas of nitrogen element utilizes plasma to activate and form the resilient coating 12 that the aggregate by column crystallization constitutes, and adopt sputtering method to form basalis 14a and the n type contact layer 14b that constitutes n type semiconductor layer 14 thereon.
The crystallization of III group-III nitride compound semiconductor has the crystalline texture of hexagonal crystal system, and forming with six prisms easily is basic set tissue.Particularly by use the plasma change the film that forms of the film build method of metal material, become column crystallization easily.At this, the column crystallization that illustrates among the present invention is meant forming crystal boundary with adjacent intergranule and separating, and self is the crystallization of column as vertical sectional shape.
Fig. 5 is transmission electron microscope (TEM) photo in the cross section of the III group-III nitride compound semiconductor laminated structure among the embodiment 1 described later, and Fig. 6 is the figure with Fig. 5 medelling.Resilient coating 12 is separated by the border of representing with solid line among Fig. 6, and each ingot between border and border is the shape of hexagonal post.In the present invention, the aggregate that such crystal habit is called column crystallization.In addition, as being distinguished by Fig. 5 and Fig. 6, such crystal habit also can be called the layer of being separated by the border, but in the present invention, also comprises such layer interior, describes as the aggregate of column crystallization.
Under the situation on the substrate 11, the semiconductor layer that is formed by III group-III nitride compound semiconductor of film forming becomes the crystalline film with well-crystallized thereon in resilient coating 12 film forming that comprise such column crystallization.
Resilient coating 12 must covered substrate 11 more than at least 60% of surperficial 11a, preferably cover more than 80%, preferably form in the mode that covers more than 90%.
In addition, resilient coating 12 most preferably in 100% the mode of covering surfaces 11a, promptly forms in the mode on the surperficial 11a of ground very close to each other covered substrate 11.
When the zone of the surperficial 11a of resilient coating 12 covered substrates 11 diminishes, become surface 11 states that expose significantly, with directly its lattice constant of basalis 14a of film forming is different on substrate 11, therefore do not become uniform crystallization at the basalis 14a of film forming on the resilient coating 12, produce hillock or hole.
In addition, the ratio of the surperficial 11a of resilient coating 12 covered substrates 11 can be measured by cross section TEM photo as shown in Figure 5.Particularly the material of resilient coating 12 and basalis 14a not simultaneously, the surface by using EDS etc. and substrate 11 is the interface of the layer on scanning substrate 11 and this substrate 11 abreast, can estimate the ratio in the zone that does not form resilient coating 12.
In addition, in the present embodiment, as described above, measure the area that substrate 11 exposes, but prepare only to have formed the sample of resilient coating 12, also can measure the area that substrate 11 exposes by methods such as AFM according to cross section TEM photo.
In addition, when on substrate 11, forming resilient coating 12, as the example that Fig. 1 represents, can form, also can form with the surperficial 11a of covered substrate 11 and the mode of side in the mode of the surperficial 11a of covered substrate 11 only.In addition, also can form in the mode at surperficial 11a, side and the back side of covered substrate 11.
Consider that from the buffering function aspects preferred resilient coating 12 is made of the aggregate of column crystallization.
The crystallization of III group-III nitride compound semiconductor has the crystalline texture of hexagonal crystal system, and forming with six prisms easily is basic set tissue.Particularly, by use the plasma change the film that forms of the film build method of metal material, become column crystallization easily.
Form like this when comprising the resilient coating 12 of column crystallization on substrate 11, the pooling feature of resilient coating 12 effectively plays a role, and therefore the III group-III nitride compound semiconductor of film forming becomes and has good crystalline crystalline film thereon.
In addition, from the aspect of buffering function, in the resilient coating 12, the mean value of the width of each crystal grain of above-mentioned column crystallization is preferably the scope of 0.1～100nm, more preferably the scope of 1～70nm.
Good for the crystallinity of the crystallizing layer that makes III group-III nitride compound semiconductor, suitably the width of each crystal grain of control column crystallization specifically, is preferably above-mentioned scope.
The width of the crystal grain of each column crystallization can easily be measured by cross section tem observation etc.That is the width of the crystal grain that is spaced apart each column crystallization on the border of each column crystallization in the ideograph represented of Fig. 6.In addition, as the TEM photo of being represented by Fig. 5 was also distinguished, the width of each column crystallization can not critically stipulate to have the distribution of width to a certain degree.Thereby the width of the crystal grain of each column crystallization has about for example several percentages even break away from the crystallization of above-mentioned scope, also can not influence effect of the present invention.In addition, the width of the crystal grain of each column crystallization preferably has more than 90% in above-mentioned scope.
The crystal grain of crystallization preferably is the roughly shape of column as described above, resilient coating 12, and the crystal grain of preferred column is gathered and cambium layer.
At this, the width of above-mentioned crystal grain when resilient coating 12 is the aggregate of columnar grain, is meant the distance at the interface and the interface of crystallization.On the other hand, when crystal grain disperseed to exist with island, the width of crystallization was meant the catercorner length of the best part of the face that crystallization crystal grain contacts with real estate.
The thickness of resilient coating 12 is preferably the scope of 10～500nm, more preferably the scope of 20～100nm.
The thickness of resilient coating 12 is during less than 10nm, and pooling feature as described above is insufficient.In addition, when forming resilient coating 12 with the thickness that surpasses 500nm, although do not change as the function of coating, the film forming processing time is elongated, worries that productivity ratio reduces.
In addition, about the bed thickness of resilient coating 12,, can easily measure according to above-mentioned cross section TEM photo.
Resilient coating 12 is preferably the composition that contains Al, is preferably especially by constituting that AlN forms.
In addition, as the material that constitutes resilient coating 12, so long as the III group-III nitride compound semiconductor of being represented by general formula AlGaInN then can use any material.And then, also can be for containing as the As of V family, the formation of P.
Making resilient coating 12 is when containing the composition of Al, wherein to be preferably GaAlN, and at this moment, the composition of Al is preferably more than 50%.
In addition, resilient coating 12 by for by constituting that AlN forms, can become the column crystallization aggregate efficiently, thereby more preferably.
In addition, as described above, resilient coating 12 can form in the mode that also covers side 11b except the surperficial 11a of covered substrate 11.And then, also can form in the mode of the back side 11c that goes back covered substrate 11.Yet, when the film build method formation resilient coating that adopts in the past, need carry out maximum about 6 times～8 times film forming and handle, become long operation.As the film build method beyond this, also can consider by substrate is not kept being arranged at indoorly, carry out the method for film forming at substrate on comprehensively, but needing the occasion of heated substrates, worry that device becomes complicated.
Therefore, for example can consider on one side by substrate being shaken or rotatablely move, and make of the sputter direction change of the position of substrate, Yi Bian carry out the method for film forming with respect to filmogen.By adopting such method, operation that can be by once then, by carrying out the film formation process to substrate back, can adopt the surface and the side film forming of substrate to add up to twice operation covered substrate comprehensive.
In addition, also can be: the filmogen source be constituting of being produced by large-area generation source, and by the occurrence positions of mobile material, moving substrate does not just carry out the method for film forming comprehensively at substrate.As such method, as described above, can list on one side by magnet being shaken or rotatablely move, on one side and the RF sputtering method of film forming carries out in the position of the magnet of swap cathode in target.In addition, when carrying out film forming, also can be the method that substrate-side and cathode side are moved by such RF sputtering method.And then, if by will be near substrate as the cathode arrangement in the generation source of material, make and not supply with the plasma that takes place to substrate, but become the formation of supplying with in the mode that substrate is wrapped into that then film forming becomes possibility substrate surface and side the time with pencil.
＜semiconductor layer 〉
As shown in Figure 1, the laminated semiconductor 10 of present embodiment, being situated between on substrate 11 has resilient coating 12 as described above and to be laminated with semiconductor layer 20, described semiconductor layer 20 have form by nitride-based compound semiconductor, n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16.
In addition, in n type semiconductor layer 14, have adopt at least sputtering film-forming, by basalis 14a and n type contact layer 14b that III group-III nitride compound semiconductor forms, on resilient coating 12, be laminated with basalis 14a.
Can form following formation: on the basalis 14a that is formed by III group-III nitride compound semiconductor, as described above, stacked laminated semiconductor shown in Figure 1 10 is such has functional crystallizing layer.For example, when being formed for the semiconductor laminated structure of light-emitting component, p type conductive layer of the p type alloy of the n type conductive layer of the n type alloy of can stackedly mix Si, Ge, Sn etc., the magnesium that mixed etc. etc. and forming.In addition,, in luminescent layer etc., InGaN can be used, in coating etc., AlGaN can be used as material.Like this, by on basalis 14a, further forming III group-III nitride compound semiconductor crystallizing layer, can make wafer making, that have semiconductor laminated structure that is used for light-emitting diode, laser diode or electronic device etc. with function.
Below, laminated semiconductor 10 is described in detail.
As nitride-based compound semiconductor, known a plurality of for example by general formula Al XGa YIn ZN 1-AM A(0≤X≤1,0≤Y≤1,0≤Z≤1, and X+Y+Z=1.Symbol M is represented and the different V group element of nitrogen (N), 0 ≦ A＜1.) gallium nitride compound semiconductor of expression, in the present invention, also can without any restrictedly use comprise gallium nitride compound semiconductor that these are known, by general formula Al XGa YIn ZN 1-AM A(0≤X≤1,0≤Y≤1,0≤Z≤1, and X+Y+Z=1.Symbol M is represented and the different V group element of nitrogen (N), 0≤A＜1.) expression gallium nitride compound semiconductor.
Gallium nitride compound semiconductor also can contain other III family element except Al, Ga and In, also can contain the element of Ge, Si, Mg, Ca, Zn, Be, P, As and B etc. as required.And then, be not limited to the element that have a mind to add, also comprise the trace impurity that contains in the impurity that exists with ... membrance casting condition and must contain and raw material, the reaction tube material sometimes.
The growing method of these gallium nitride compound semiconductors is not particularly limited, except above-mentioned sputtering method, the known whole method that makes nitride semiconductor growing of also applicable MOCVD (Metalorganic Chemical Vapor Deposition), HVPE (hydride vapor growth method), MBE (molecular beam epitaxy) etc.As preferred growing method,, be mocvd method from the viewpoint of film thickness monitoring, production.In mocvd method, can use hydrogen (H as carrier gas 2) or nitrogen (N 2), can use trimethyl gallium (TMG) or triethyl-gallium (TEG) as the Ga source of III family raw material, can use trimethyl aluminium (TMA) or triethyl aluminum (TEA) as the Al source, can use trimethyl indium (TMI) or triethylindium (TEI) as the In source, as the nitrogenous source of V family raw material, can use ammonia (NH 3), hydrazine (N 2H 4) etc.In addition, as alloy, in the n type, can use monosilane (SiH as the Si raw material 4) or disilane (Si 2H 6), can use germane gas (GeH as the Ge raw material 4), tetramethyl germanium ((CH 3) 4Ge), tetraethyl germanium ((C 2H 5) 4Ge) etc. organic germanium compounds.In the MBE method, the germanium of element state also can be used as doped source and uses.In the p type, for example use bis-cyclopentadienyl magnesium (Cp as the Mg raw material 2Mg) or two ethyl cyclopentadienyl group magnesium (EtCp 2Mg).
[n type semiconductor layer]
N type semiconductor layer 14 is laminated on the above-mentioned resilient coating 12 usually, is made of basalis 14a, n type contact layer 14b and n type coating 14c.In addition, but n type contact layer double as is basalis and/or n type coating.
(basalis)
The basalis 14a of present embodiment is formed by III group-III nitride compound semiconductor, can be by aforesaid sputtering method stacked ground film forming on resilient coating 12.
As the material of basalis 14a, may not be identical with the resilient coating 12 of film forming on substrate 11, also can use different materials, preferably by Al xGa 1-xN layer (0≤x≤1 is preferably 0≤x≤0.5, more preferably 0≤x≤0.1) constitutes.
The result that the inventor etc. experimentize is clear and definite, as the material that in basalis 14a, uses, preferably contain Ga III group-III nitride compound, be the GaN based compound semiconductor.
Above-mentioned resilient coating 12 for forms by AlN constitute the time, basalis 14a must make the dislocation cyclisation by migration, so that the succession of former state ground is not as the crystallinity of the resilient coating 12 of the aggregate of column crystallization.As the material of the cyclisation that is easy to generate dislocation, can enumerate the GaN based compound semiconductor that comprises Ga, preferred especially AlGaN or GaN.
The thickness of basalis 14a is preferably more than the 0.1 μ m, more preferably more than the 0.5 μ m, most preferably is more than the 1 μ m.When this thickness is above, obtain the good Al of crystallinity easily xGa 1-xThe N layer.
In basalis 14a, as required, can mix 1 * 10 17～1 * 10 19/ cm 3Scope in n type impurity, but also can undope (＜1 * 10 17/ cm 3), consider from keeping good crystalline aspect, preferably undope.
When substrate 11 is conductivity, form conductivity by doping alloy in basalis 14a, can be at the electrode of formation up and down of light-emitting component.On the other hand, when using the material of insulating properties in basic 11, become the chip structure that is provided with each electrode of anodal and negative pole in the identical faces of light-emitting component, so basalis 14a do not need to mix, crystallinity becomes good thereby preferably when undoping.
As n type impurity, be not particularly limited, can enumerate for example Si, Ge and Sn etc., preferably enumerate Si and Ge.
When using the substrate of conductivity in substrate 11, as described above, 14a mixes to basalis, and the layer structure that makes basalis 14a can form the structure that electrode is set on the chip two sides of light-emitting component in the longitudinal stream overcurrent.
In addition, when in substrate 11, using the insulating properties substrate, adopt chip structure at the identical surface forming electrode of the chip of light-emitting component, therefore on substrate 11, be situated between resilient coating 12 is arranged and stacked basalis 14a when not have the crystallization of doping, it is good that crystallinity becomes.
When adopting sputtering method to form basalis 14a, come the method for film forming in reactor, can keep crystallinity well, can stably reproduce this good crystallinity by the control reaction by the reactive sputtering method that the nitride raw material is circulated, thereby more preferably.
In addition, when adopting sputtering method to form basalis 14a, compare, can make device become easy formation with mocvd method, MBE method etc.
The temperature of the substrate 11 when forming basalis 14a, promptly the growth temperature of basalis 14a is preferably the temperature more than 800 ℃.This is because pass through to improve the temperature of the substrate 11 when forming basalis 14a, is easy to generate the migration of atom, and the cyclisation of dislocation is carried out easily.In addition, the temperature of the substrate 11 when forming basalis 14a is necessary for the low temperature of temperature of decomposing than crystallization, therefore is preferably less than 1200 ℃.If the temperature of the substrate 11 when forming basalis 14a then can obtain the good basalis 14a of crystallinity in the said temperature scope.
(n type contact layer)
The n type contact layer 14b of present embodiment is formed by III group-III nitride compound semiconductor, by above-mentioned sputtering method stacked ground film forming on basalis 14a.
As n type contact layer 14b, with basalis 14a similarly preferably by Al xGa 1-xN layer (0≤x≤1, preferred 0≤x≤0.5, further preferred 0≤x≤0.1) constitutes.In addition, preferably be doped with n type impurity, when with 1 * 10 17～1 * 10 19/ cm 3Concentration, preferably with 1 * 10 18～1 * 10 19/ cm 3Concentration when containing n type impurity, be preferred from keeping with the good Ohmic contact of negative pole, suppressing that crackle takes place, keeps good crystalline viewpoint.As n type impurity, be not particularly limited, can enumerate for example Si, Ge and Sn etc., be preferably Si and Ge.Growth temperature and basalis 14a are same.In addition, as described above, n type contact layer 14b can be the formation of double as basalis.
Constitute the gallium nitride compound semiconductor of basalis 14a and n type contact layer 14b, be preferably same composition, their total thickness is set at 0.1～20 μ m, be preferably set to 0.5～15 μ m, further be preferably set to the scope of 1～12 μ m.When thickness during, can keep semi-conductive crystallinity well in this scope.
(n type coating)
Between said n type contact layer 14b and luminescent layer described later 15, n type coating 14c is set preferably.By n type coating 14c is set, but landfill results from the deterioration of the most surperficial flatness of n type contact layer 14b.N type coating 14c can use known mocvd method etc. in the past, utilizes film forming such as AlGaN, GaN, GaInN.In addition, also can be the heterojunction of these structures or repeatedly stacked superlattice structure.When being GaInN, certainly preferably the band gap than the GaInN of luminescent layer 15 is big.
The thickness of n type coating 14c is not particularly limited, but is preferably the scope of 5～500nm, the more preferably scope of 5～100nm.
In addition, the n type concentration of dopant of n type coating 14c is preferably 1 * 10 17～1 * 10 20/ cm 3Scope, more preferably 1 * 10 18～1 * 10 19/ cm 3Scope.Concentration of dopant considers it is preferred from the aspect of keeping good crystallinity and reducing the operating voltage of light-emitting component when this scope.
" p type semiconductor layer "
P type semiconductor layer 16 is made of p type coating 16a and p type contact layer 16b usually, can use known in the past mocvd method to wait film forming.In addition, also can be that p type contact layer double as is the formation of p type coating.
(p type coating)
As p type coating 16a,, can preferably enumerate Al so long as be that the charge carrier that can seal to luminescent layer 15 just is not particularly limited than the big composition of band-gap energy of the luminescent layer 15 of aftermentioned details dGa 1-dThe composition of N (0＜d≤0.4, preferred 0.1≤d≤0.3).When p type coating 16a is formed by such AlGaN, in sealing to being preferred aspect the charge carrier of luminescent layer 15.The thickness of p type coating 16a is not particularly limited, but is preferably 1～400nm, more preferably 5～100nm.The p type concentration of dopant of p type coating 16a is preferably 1 * 10 18～1 * 10 21/ cm 3, more preferably 1 * 10 19～1 * 10 20/ cm 3P type concentration of dopant can not reduce crystallinity and obtains good p type crystallization when this scope.
(p type contact layer)
As p type contact layer 16b, be to comprise Al at least eGa 1-eThe gallium nitride system compound semiconductor layer of N layer (0≤e＜0.5, preferred 0≤e≤0.2, further preferred 0≤e≤0.1).When Al consisted of above-mentioned scope, good crystallinity reached and the aspect of the good Ohmic contact of p Ohmic electrode (with reference to optically transparent electrode 17 described later) is preferred from keeping.
In addition, when with 1 * 10 18～* 10 21/ cm 3The concentration of scope when containing p type alloy, from keep with the good Ohmic contact of negative pole, suppressing crackle, good crystalline viewpoint takes place, keeps is preferred, more preferably 5 * 10 19～5 * 10 20/ cm 3Scope.
As p type impurity, be not particularly limited, can preferably enumerate for example Mg.
The thickness of p type contact layer 16b is not particularly limited, and is preferably 10～500nm, more preferably 50～200nm.Thickness is preferred from the viewpoint of luminous power output when this scope.
＜luminescent layer 〉
Luminescent layer 15 is to be laminated on the p type semiconductor layer 14, and the stacked top layer with it of p type semiconductor layer 16, can use in the past known mocvd method etc. to carry out film forming.In addition, luminescent layer 15, as shown in Figure 1, be that the trap layer 15b that form with the barrier layer 15a that will be formed by gallium nitride compound semiconductor with by the gallium nitride compound semiconductor that contains indium is alternately stacked repeatedly, and in the sequential cascade ground formation of n type semiconductor layer 14 sides and p type semiconductor layer 16 sides configuration barrier layer 15a.
In addition, in the example that Fig. 1 represents, luminescent layer 15 is following formation: the trap layer 15b of 6 layers barrier layer 15a and 5 layers is alternately stacked repeatedly, at the superiors and the orlop configuration barrier layer 15a of luminescent layer 15, configuration trap layer 15b between each barrier layer 15a.
As barrier layer 15a, for example can preferably use band-gap energy than the big Al of trap layer 15b that forms by the gallium nitride compound semiconductor that contains indium cGa 1-cThe gallium nitride compound semiconductor of N (0≤c＜0.3) etc.
In addition, in trap layer 15b,, for example can use Ga as the gallium nitride compound semiconductor that contains indium 1-sIn sThe indium gallium nitride of N (0＜s＜0.4) etc.
In addition,, be not particularly limited, preferably can obtain quantum and imitate the thickness of hard degree, be critical film thickness as the overall thickness of luminescent layer 15.For example, the thickness of luminescent layer 15 is preferably the scope of 1～500nm, more preferably the thickness about 100nm.Thickness helps to improve luminous power output when above-mentioned scope.
＜light transmission positive pole 〉
Light transmission positive pole 17 is electrodes of the light transmission of formation on the p type semiconductor layer 16 of the laminated semiconductor of making as described above 10.
Material as the transparency anodal 17 is not particularly limited, and the customary means of knowing in available this technical field is provided with ITO (In 2O 3-SnO 2), AZO (ZnO-Al 2O 3), IZO (In 2O 3-ZnO), GZO (ZnO-Ga 2O 3) material that waits.
In addition, its structure also can comprise any structure of known structure in the past without any restrictedly using.
Light transmission positive pole 17 can form in roughly whole mode on the p semiconductor layer 16 that covers doped with Mg, can also vacate the gap and form with trellis, tree shape.After forming light transmission positive pole 17, implement sometimes with alloying or the transparent thermal annealing that turns to purpose, but also can not implement.
＜positive terminal pad and negative pole 〉
Positive terminal pad 18 is the electrodes that form on above-mentioned light transmission positive pole 17.
As the material of positive terminal pad 18, the various structures of having used Au, Al, Ni and Cu etc. are arranged as everyone knows, can be without any the positive terminal pad of restrictedly using these material known, structure.
The thickness of positive terminal pad 18 is preferably in the scope of 100～1000nm.In addition, on the characteristic of pad, when its thickness was big, zygosity increased, so the thickness of positive terminal pad 18 is more preferably more than the 300nm.And then the viewpoint from manufacturing cost is preferably below the 500nm.
Negative pole 19 stacks gradually on substrate 11 in the semiconductor layer of n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16, forms in the mode that contacts with the n type contact layer 14b of n type semiconductor layer 14.
For this reason, when forming negative terminal pad 17, remove the part of luminescent layer 15, p type semiconductor layer 16 and n type semiconductor layer 14, form the regional 14d that exposes of n type contact layer 14b, form negative pole 19 thereon.
As the material of negative pole 19, the negative pole of various The Nomenclature Composition and Structure of Complexes is well-known.Can utilize the customary means of in this technical field, knowing to be provided with without any restrictedly using these known negative poles.
Manufacture method according to the III group-III nitride compound semiconductor light-emitting device of as described above present embodiment by above-mentioned formation, can adopt sputtering method to form the crystalline film that has good uniformity at short notice.Thus, can stably form the good III group-III nitride compound semiconductor layer of crystallinity.
The manufacture method of present embodiment, by under these conditions, at least use sputtering method form to constitute the basalis 14a and the n type contact layer 14b of the n type semiconductor layer 14 among the layer of semiconductor layer 20, can generate high bias voltage or high-power reactive material thus, and can supply with this reactive material to substrate 11 with high kinergety, therefore on substrate 11, move, easily with the dislocation cyclisation.Thus, the basalis 14a of n type semiconductor layer 14, can former state ground inherit on substrate 11 film forming as the crystallinity of the resilient coating 12 of the aggregate of column crystallization.Thus, can form the good semiconductor layer that forms by III group-III nitride compound of crystallinity.
In addition, in the present embodiment, use sputtering method to form semiconductor layer at least, therefore can improve film forming speed, can shorten film forming (manufacturing) time.And then by shortening manufacturing time, the indoor situation that impurity can be entered in the sputter equipment suppresses to be Min..
Thereby, the III group-III nitride compound semiconductor light-emitting device that can obtain the productivity ratio excellence and have the excellent characteristics of luminescence.
[lamp]
As described above, can utilize the means that well known to a person skilled in the art to constitute lamp by combination III group-III nitride compound semiconductor light-emitting device of the present invention and fluorophor.All the time, known have a technology that changes illuminant colour by illuminated in combination element and fluorophor, can be without any restrictedly adopting such technology.
For example, by suitable selected fluorophor, can obtain the luminous of the wavelength longer than light-emitting component, in addition, the emission wavelength by mixed luminescence element self and by the wavelength of fluorophor conversion can be made into and presents white luminous lamp.
In addition, as lamp, can be used for any purposes of lateral emitting (side view) type of general purpose bullet cut, portable purposes backlight, top light emitting (top view) type that in display, uses etc.
For example, as the example that Fig. 4 represents, in the time of will being mounted to bullet cut with the III group-III nitride compound semiconductor light-emitting device 1 of an electrode type, one (being frame 31 among Fig. 4) in two frames gone up bonding light-emitting component 1, in addition, engage with frame 32 with the negative pole (with reference to the symbol of representing among Fig. 3 19) of line 34, engage with frame 31 with the positive terminal pad (with reference to the symbol of representing among Fig. 3 18) of line 33 with light-emitting component 1 with light-emitting component 1.Then, the periphery of light-emitting component 1 is carried out molding, can be made into the lamp 3 of bullet cut shown in Figure 4 by the mold 35 that forms by transparent resin.
In addition, III group-III nitride compound semiconductor light-emitting device of the present invention except above-mentioned light-emitting component, also can be used for the photo-electric conversion element of laser diode, photo detector etc. or the electronic device of HBT, HEMT etc. etc.The known semiconductor element that multiple various structures are arranged of these semiconductor elements, the component structure of the laminated structure of III group-III nitride compound semiconductor light-emitting device of the present invention comprises these known elements structures and without any restriction.
Embodiment
Then, be described in more detail the manufacture method of III group-III nitride compound semiconductor light-emitting device of the present invention by embodiment, but the present invention not only is defined in these embodiment.
[embodiment 1]
Fig. 1 represents the cross section ideograph of the laminated semiconductor of the III group-III nitride compound semiconductor light-emitting device that this experimental example is made.
In this example, on the c face of the substrate 11 that constitutes by sapphire, use the RF sputtering method to form the aggregate of the column crystallization that forms by AlN,, use the RF sputtering method to form the layer that forms by GaN thereon as basalis 14a as resilient coating 12.
At first, by only one side being carried out the substrate 11 that mirror ultrafinish to the sapphire that can be used for epitaxially grown degree constitutes, do not carry out the pre-treatment of wet type particularly etc. and import in the sputter equipment.Here,, used to have the high frequency type power supply as sputter equipment, and have can be in target the device of the mechanism of the position of moving magnet.
Then, in sputter equipment, substrate 11 is heated to 750 ℃, only import nitrogen with the flow of 15sccm after, indoor pressure is remained on 0.08Pa, apply the high frequency bias of 50W in substrate 11 sides, be exposed in the nitrogen plasma, wash substrate 11 surfaces thus.
Then, after in sputter equipment, importing argon and nitrogen, make the temperature of substrate 11 be reduced to 500 ℃.Then, apply 0.5W/cm in substrate 11 sides 2High frequency bias the time, apply 1W/cm in metal A l target side 2Power, keeping the pressure in the stove is 0.5Pa, under with 5sccm circulation argon gas, condition with 15sccm circulation nitrogen (ratio of nitrogen in gas is all is 75%), forms the resilient coating 12 that is made of AlN on the substrate 11 that is made of sapphire.The speed of growth is 0.12nm/ second.
Magnet in the time of washing arbitrary during substrate 11 and during film forming in the rotary target.
Then, carry out the processing of stipulated time, behind the AlN film (resilient coating 12) of formation 50nm, stop plasma work, reduce the temperature of substrate 11 according to the film forming speed of measuring in advance.
Then, from sputter equipment, take out the substrate 11 that has formed resilient coating 12, be transported in the other sputter equipment, use sputtering method to form the sample of GaN layer (III group-III nitride semiconductor) according to following sequentially built.Here,, use to have high-frequency power supply, and have by magnet and scan in the dimetric Ga target device of the mechanism of the position that removable magnetic field applies as the sputter equipment that forms the GaN layer.In addition, the pipe arrangement of circulation refrigerant is set in the Ga target, the refrigerant that is cooled to 20 ℃ is circulated in pipe arrangement, prevent the fusing of the Ga that causes by heat.
At first, behind indoor importing argon gas and nitrogen, the temperature of substrate 11 is warming up to 1000 ℃.Then, apply 0.5W/cm in substrate 11 sides 2High frequency bias, simultaneously apply 1W/cm in metal Ga target side 2Power, when the pressure in the holding chamber is 0.5Pa, under with 5sccm circulation argon gas, condition (ratio of nitrogen in gas is all is 75%) with 15sccm circulation nitrogen, on the substrate 11 that constitutes by sapphire, forms by GaN constitute layer.The speed of growth of this moment is approximately 0.12nm/ second.Then, form the GaN layer of 6 μ m after, stop to produce plasma.
Then, under same condition, formation has 1 * 10 19Cm -3The GaN layer of doping Si of 2 μ m of electron concentration.Each condition of film forming and unadulterated GaN layer are same, towards being arranged at indoor Si target, shining the ion of being emitted by ion gun and take out Si, doping Si.
By above operation, on the substrate 11 that constitutes by sapphire, form have column structure, by the resilient coating 12 that AlN constitutes, form the GaN layer (basalis 14a) of the thickness of 6 μ m thereon with unadulterated form, form thereon again and have 1 * 10 19Cm -3The GaN layer (n type contact layer 14b) of doping Si of 2 μ m of electron concentration, made the sample of embodiment 1.This specimen surface presents water white specular.
Then, use X ray analyzer (パ Na リ テ イ カ Le society system; Four crystallization X ray determinators, model: X ' pert) measure the X ray swing curve (XRC) of the unadulterated GaN layer (basalis 14a) that obtains by said method.This measure to use Cu β ray X ray the source to take place as light source, is carrying out as (0002) face of the plane of symmetry with as (11-20) face of asymmetric.Usually, under the situation of III group-III nitride compound semiconductor, the wide index that becomes the flatness (モ ザ イ シ テ イ) of crystallization of the XRC spectrum half value of (0002) face, (11-20) wide dislocation density (helical form that becomes of the XRC spectrum half value of face; Twist) index.The result of this mensuration, the unadulterated GaN layer that utilizes manufacture method of the present invention to make shows the wide 180arcsec of half value in the mensuration of (0002) face, show the wide 300arcsec of half value for (11-20) face.
[embodiment 2]
In this example, in the unadulterated GaN crystallization (basalis 14a) of 6 μ m of film forming under the condition similarly to Example 1, use identical sputter equipment, form the n type contact layer 14b of the Si that mixed.
Then, sample is imported in the MOCVD stove, form each layer on it, finally made the epitaxial wafer with epitaxial layer structure (laminated semiconductor 10) that the III group-III nitride compound semiconductor light-emitting device represented as Fig. 1 is used.
This epitaxial wafer has following structure: on the substrate 11 that is made of the sapphire with c face, by growing method similarly to Example 1, formation begins sequentially stacked from substrate 11 sides after having the resilient coating 12 that is made of AlN of column structure: the basalis 14a that is formed by unadulterated GaN of 6 μ m, by having 1 * 10 19Cm -3The n type contact layer 14b that constitutes of the GaN of 2 μ m of electron concentration by doping Si, have 1 * 10 18Cm -3The In of 20nm of electron concentration 0.1Ga 0.9N type coating (n type coating 14c), start from the GaN barrier layer and end at the GaN barrier layer laminated construction, alternately to be laminated with bed thickness be the unadulterated In that 6 layers barrier layer 15a constituting of the GaN of 16nm and bed thickness are 3nm 0.2Ga 0.8The luminescent layer (multi-quantum pit structure) 15 that 5 layers the trap layer 15b that N constitutes forms, Al by doped with Mg with 5nm 0.1Ga 0.9 P type coating 16a that N constitutes and the Al of thickness 200nm by doped with Mg 0.02Ga 0.98The p type semiconductor layer 16 of the p type contact layer 16b that N constitutes.
By above order, make the epitaxial wafer that semiconductor light-emitting elements is used with epitaxial layer structure.Here, by the Al of doped with Mg 0.02Ga 0.98The p type contact layer 16b that N constitutes even be not used for annealing in process with p type carrier activation, also demonstrates p type characteristic.
Then, use the epitaxial wafer that on the substrate 11 that constitutes by sapphire, is laminated with epitaxial layer structure (with reference to the laminated semiconductor 10 of Fig. 1) as described above, make a kind of light-emitting diode (with reference to the light-emitting component 1 of Fig. 2 and Fig. 3) as semiconductor light-emitting elements.
At first, for the wafer of making, by known photoetching process at Al by doped with Mg 0.02Ga 0.98On the surface of the p type contact layer 16b that N constitutes, form the light transmission positive pole 17 that constitutes by ITO and have thereon from the anodal face side positive terminal pad 18 of structure of Ti, Al, Au that begun sequential cascade.In addition, the part of wafer is implemented dry ecthing, expose the regional 14d that exposes on the n type contact layer 14b, on this part, make by these 4 layers of negative poles that constitutes 19 of Ni, Al, Ti and Au.By these operations, on wafer, made each electrode with shape of representing as Fig. 2 and Fig. 3.
For this has formed the wafer of electrode on two-layer in p type semiconductor layer and n type semiconductor layer as described above, grind the dorsal part of cutting and grind substrate 11, make specular face, cut into the square foursquare chip of 350 μ m, each electrode up mounting on lead frame, by being connected in lead frame, made semiconductor light-emitting elements with gold thread.The forward current that circulates between the electrode of the positive terminal pad 18 of this semiconductor light-emitting elements (light-emitting diode) and negative pole 19, the forward voltage under the electric current 20mA is 3.0V.In addition, observe luminance by the light transmission anodal 17 of p side, emission wavelength is 470nm, and luminous power output shows 15mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of the roughly whole making of the wafer of making, does not obtain with can having deviation.
[embodiment 3]
In this example, on the c of the substrate that constitutes by sapphire face, as resilient coating, the RF sputter equipment of use rotating cathode formula forms the aggregate of the column crystallization of AlN, sputter equipment identical when utilizing the resilient coating that is made of AlN with formation thereon, forms GaN layer (basalis 14a and n type contact layer 14b).Then, adopt mocvd method to form the light-emitting component semiconductor laminated structure similarly to Example 2 thereon.
The temperature of the substrate during the sputter resilient coating is 700 ℃, and the temperature of the substrate when forming basalis is 900 ℃.Other membrance casting condition is all identical with embodiment 2.
Then, take out wafer from reaction unit, the surface that can confirm wafer is a minute surface.
Then, use cross section TEM method to observe above-mentioned wafer.By the AlN layer (resilient coating) of RF spatter film forming, that can confirm to become crystal grain widely is the column crystallization about 50nm.In addition, whole of resilient coating covered substrate and forming.
Then, with the wafer of making as described above, make light-emitting diode chip for backlight unit similarly to Example 2.The forward current that circulates between electrode, the forward voltage under the electric current 20mA is 3.1V.In addition, luminous by anodal 17 observations of the light transmission of p side, emission wavelength is 460nm, and luminous power output shows 13mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of the roughly whole making of the wafer of making, does not obtain with can having deviation.
[embodiment 4]
In this example, on Si (111) substrate, as resilient coating, the RF sputter equipment of use rotating cathode formula forms the aggregate of the column crystallization of AlGaN, thereon, as basalis, use the device identical to form the AlGaN layer of doping Si with embodiment 1, and then formation light-emitting component semiconductor laminated structure similarly to Example 2 thereon.Here, the Al of resilient coating consists of 70%, and the Al of basalis consists of 15%.In addition, the temperature of the substrate during sputter is 500 ℃, and the film-forming temperature of basalis is 700 ℃.Other membrance casting condition is all identical with embodiment 1.
In embodiment 4, grow the light-emitting component semiconductor laminated structure after, from reaction unit, take out wafer, the surface that can confirm wafer is a minute surface.
Then, use cross section TEM method to observe above-mentioned wafer.By the GaAlN layer (resilient coating) of RF spatter film forming, the width that can confirm to become crystal grain is the column crystallization about 30nm.In addition, whole of resilient coating covered substrate and forming.
Then, with the wafer of making as described above, make light-emitting diode chip for backlight unit similarly to Example 2.In this example, in the upper and lower settings of semiconductor laminated structure side and substrate-side each electrode, the forward current that circulates between electrode, the forward voltage under the electric current 20mA are 2.9V.
In addition, luminous by the anodal observation of the light transmission of p side, emission wavelength is 460nm, and luminous power output shows 10mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of the roughly whole making of the wafer of making, does not obtain with can having deviation.
[embodiment 5]
In this example, on ZnO (0001) substrate, as resilient coating, use the RF magnetron sputtering method to form the aggregate of the column crystallization of GaN, thereon, as basalis, use the device identical to form the layer of the AlGaN of doped with Ge, and then adopt method formation light-emitting component semiconductor laminated structure similarly to Example 2 thereon with embodiment 1.
Here, the Al of basalis consists of 10%.In addition, the temperature of the substrate when carrying out the sputter of resilient coating is a room temperature, and the temperature of the substrate when carrying out the basalis film forming is 750 ℃.In addition, in this example,, increased the material flow of the In that contains in the luminescent layer in order to attempt making near the green LED the 525nm.
In embodiment 5, grow the light-emitting component semiconductor laminated structure after, from reaction unit, take out wafer, the surface that can confirm wafer is a minute surface.
Then, use cross section TEM method to observe above-mentioned wafer.GaN layer, the width that can confirm to become crystal grain are the column crystallization about 5nm.In addition, whole of resilient coating covered substrate and forming.
Then,, adopt method similarly to Example 2 to make light-emitting diode chip for backlight unit with the wafer of making as described above, in addition, similarly to Example 4 in the upper and lower settings of laminated construction side and substrate-side each electrode.Then, the forward current that circulates between electrode, the forward voltage under the electric current 20mA are 3.3V.In addition, luminous by the anodal observation of the light transmission of p side, emission wavelength is 525nm, and luminous power output shows 10mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of the roughly whole making of the wafer of making, does not obtain with can having deviation.
By above result as can be known, III group-III nitride compound semiconductor light-emitting device of the present invention, the productivity ratio excellence, and have the excellent characteristics of luminescence.
(second execution mode)
In the present embodiment, for the item beyond the item of following record, identical with above-mentioned first execution mode.
In the present embodiment, as the important parameter that uses in the sputtering film-forming, can enumerate bias voltage, put on pressure in the power, substrate temperature, stove of target, nitrogen partial pressure, film forming speed etc.
In the manufacture method of present embodiment, when forming semiconductor layer with sputtering method, the bias value that puts on substrate 11 is preferably 0.1W/cm 2More than, 0.2W/cm more preferably 2More than, most preferably be 0.5W/cm 2More than.
By making the bias value that puts on the substrate 11 is above-mentioned scope, can generate high bias reactive material, in addition, can supply with these reactive materials to substrate 11 with high kinergety, so the migration on the substrate 11 comes to life, and makes the dislocation cyclisation easily.
In addition, in the manufacture method in execution mode, when forming semiconductor layer with sputtering method, the power that puts on metallic target (sputtering target) 47 is preferably 0.1W/cm 2～100W/cm 2Scope, 1W/cm more preferably 2～50W/cm 2Scope, most preferably be 1.5W/cm 2～50W/cm 2Scope.
By making the power that puts on metallic target 47 is above-mentioned scope, and generates the reactive material of big power, in addition, can supply with these reactive materials to substrate 11 with high kinergety, so the migration on the substrate 11 comes to life, and makes the dislocation cyclisation easily.
(the 3rd execution mode)
For the item beyond the item of following record, identical with above-mentioned first execution mode.
The manufacture method of present embodiment is when forming above-mentioned semiconductor layer, in the chamber that is used for sputter (with reference to the symbol 41 of Fig. 7), supplies with nitrogen (N 2) and argon (Ar) method of carrying out sputter.
In addition, the manufacture method of present embodiment is when forming above-mentioned semiconductor layer, and making above-mentioned indoor pressure is the following method of 10Pa.
In addition, the manufacture method of present embodiment is that temperature when forming above-mentioned semiconductor layer, aforesaid substrate is the method for 400 ℃～1300 ℃ scope.
In addition, the manufacture method of present embodiment is that film forming speed when forming above-mentioned semiconductor layer is the method for the scope of 0.1～10nm/ second.
In addition, resilient coating 12 can form in the mode that also covers the side except the surperficial 11a of substrate 11, and then, also can form in the mode at the back side of going back covered substrate 11.
Negative pole 19 stacks gradually on substrate 11 in the semiconductor layer of n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16, forms in the mode that contacts with the n type contact layer 14b of n type semiconductor layer 14.
Therefore, when negative pole 19 is set,, form the regional 14d that exposes of n type contact layer 14b, form negative pole 19 thereon by removing the part of p type semiconductor layer 16, luminescent layer 15 and n type semiconductor layer 14.
As the material of negative pole 19, the negative pole of various The Nomenclature Composition and Structure of Complexes is known, can be without any restrictedly using these known negative poles, and can utilize customary means known in this technical field to be provided with.
[manufacture method of light-emitting component]
Below, an example of the manufacture method of the light-emitting component of representing for Fig. 2 and Fig. 31 describes.
The manufacture method of light-emitting component of the present invention as described above, is to be included on the substrate 11 to adopt sputtering method to form the method for the operation of the semiconductor layer that is made of the III group-III nitride compound semiconductor that contains as the Ga of III family element.
In order to use sputtering method on substrate 11, to form the III group-III nitride compound semiconductor layer of crystallinity excellence, must generate more high-octane reactive material, make the migration on the substrate active, be the method for following detailed description in the present embodiment therefore.
＜manufacture method of laminated semiconductor 〉
In the manufacture method of present embodiment, on substrate 11, make the crystallization of III group-III nitride compound semiconductor carry out epitaxial growth, when forming laminated semiconductor 10 as shown in Figure 1, on substrate 11, form resilient coating 12, form semiconductor layer 20 thereon.In the present embodiment, constitute among each layer of semiconductor layer 20, adopt sputtering method to form basalis 14a and the n type contact layer 14b that constitutes n type semiconductor layer 14.Then, use mocvd method to form n type coating 14c, luminescent layer 15, the p type coating 16a that constitutes p type semiconductor layer 16 and each layer of p type contact layer 16b of formation n type semiconductor layer 14 thereon.
" formation of resilient coating "
When on substrate 11, forming resilient coating 12, preferably substrate 11 is carried out the pre-treatment of wet type.For example, for the substrate 11 that is made of silicon, the RCA washing methods that enforcement is known makes the surface be the hydrogen terminal, makes film-forming process stable.
In addition, before importing back in the reactors at substrate 11, forming resilient coating 12, can use the method for sputtering method etc. to carry out pre-treatment.Specifically, by substrate 11 is exposed to Ar, N 2Plasma in put the surface in order.For example, the action of plasma by making argon gas, nitrogen etc. can be removed the organic substance and the oxide that are attached to substrate 11 surfaces in substrate 11 surfaces.At this moment, if apply voltage between substrate 11 and chamber, then plasma particle acts on substrate 11 efficiently.
After carrying out the pre-treatment on substrate 11 surfaces, in sputter equipment, import argon gas and nitrogen, reduce about the temperature to 500 ℃ of substrate 11.Then, when substrate 11 sides apply high frequency bias, apply power, the pressure in the stove is remained certain the time, on substrate 11, form the resilient coating 12 that constitutes by AlN in the Al target side that constitutes by metal A 1.
On substrate 11, form the method for resilient coating 12, be not particularly limited, except sputtering method, for example can enumerate mocvd method, pulsed laser deposition (PLD) method, pulsed electron beam deposition (PED) method etc., can suitably select to use, but, be preferable methods therefore because sputtering method is the easiest and be suitable for volume production.In addition, when using the DC sputter, can cause the charging on target surface, have the unsettled possibility of film forming speed, therefore be preferably pulsed D C sputtering method or RF sputtering method.
The resilient coating 12 of film forming on substrate 11 preferably to contain the composition film forming of Al, especially preferably carries out film forming with the composition that contains AlN.In addition, as the material that is used for resilient coating 12, so long as the III group-III nitride compound semiconductor of being represented by general formula AlGaInN then can use any material.And then, also can form the As that contains as V family, the composition of P carries out film forming.
Making resilient coating 12 is when containing the composition of Al, wherein to be preferably GaAlN, and at this moment, the composition of Al is preferably more than 50%.
In addition,, can become the column crystallization aggregate efficiently by form resilient coating 12 by AlN, thereby more preferably.
In addition, as described above, resilient coating 12 can form in the mode that also covers the side except the surperficial 11a of covered substrate 11, and then, also can form in the mode at the back side of going back covered substrate 11.
But when adopting film build method formation resilient coating in the past, the film forming that need carry out at most about 6 times～8 times is handled, and becomes long operation.As the film build method beyond this, also can consider by substrate is not kept being arranged at indoorly, carry out the method for film forming at substrate comprehensively, but when the needs heated substrates, worry that device becomes complicated.
Therefore, for example can consider on one side by substrate being shaken or rotatablely move, with respect to the position of the sputter direction change substrate of filmogen, Yi Bian carry out the method for film forming.According to such method, can adopt once operation with the surface and the side film forming of substrate, then by carrying out film formation process to substrate back, can be to add up to twice operation covered substrate comprehensive.
In addition, filmogen source (target) is constituting of being produced by large-area generation source, and, by the occurrence positions of mobile material, moving substrate and getting final product not in the method that substrate carries out film forming comprehensively.As such method, can list, as described above, on one side by magnet being shaken or rotatablely move, the position of the magnet of swap cathode in target is carried out the RF sputtering method of film forming on one side.
In addition, when carrying out film forming, can adopt the method for moving substrate side and cathode side by such RF sputtering method.And then by will the plasma that takes place not being supplied in substrate with pencil, but becoming the formation of supplying with in the mode that substrate is wrapped into as the cathode arrangement in the generation source of material near substrate, film forming becomes possibility in the time of substrate surface and side.
" formation of semiconductor layer "
By on resilient coating 12, stack gradually n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16, and form semiconductor layer 20.In the manufacture method of present embodiment, as described above, among each layer that constitutes semiconductor layer 20, use sputtering method to form basalis 14a and the n type contact layer 14b that constitutes n type semiconductor layer 14, in addition, use mocvd method to form n type coating 14c, luminescent layer 15 and p type semiconductor layer 16.
Growing method as gallium nitride compound semiconductor, can enumerate MOCVD (Metalorganic Chemical Vapor Deposition), HVPE (hydride vapor growth method), MBE (molecular beam epitaxy) etc., from the preferred mocvd method of the viewpoint of film thickness monitoring, production.In mocvd method, can use hydrogen (H as carrier gas 2) or nitrogen (N 2), as III family raw material, trimethyl gallium (TMG) or triethyl-gallium (TEG) can be used in the Ga source, can use trimethyl aluminium (TMA) or triethyl aluminum (TEA) as the Al source, trimethyl indium (TMI) or triethylindium (TEI) can be used as the In source, ammonia (NH can be used as the nitrogenous source of V family raw material 3) or hydrazine (N 2H 4) etc.In addition, as alloy, in the n type, can use monosilane (SiH as the Si raw material 4) or disilane (Si 2H 6), can use germane gas (GeH as the Ge raw material 4), tetramethyl germanium ((CH 3) 4Ge), tetraethyl germanium ((C 2H 5) 4Organic germanium compounds such as Ge).In the MBE method, also can utilize the germanium of element state as doped source.In the p type, for example can use bis-cyclopentadienyl magnesium (Cp as the Mg raw material 2Mg), two ethyl cyclopentadienyl group magnesium (EtCp 2Mg).
(formation of basalis and n type contact layer)
When forming the semiconductor layer 20 of present embodiment, at first, adopt sputtering method on resilient coating 12, to form the basalis 14a of n type semiconductor layer 14 stackedly.In addition, on basalis 14a, and then adopt sputtering method to form n type contact layer 14b stackedly.
In the manufacture method of present embodiment, adopted when forming basalis 14a and n type contact layer 14b, to the indoor supply nitrogen and the argon that are used for sputter, the operation of carrying out sputter.
In the manufacture method of present embodiment, the sputter equipment 40 that for example can use Fig. 7 to represent forms basalis 14a and n type contact layer 14b.The sputter equipment 40 of illustrated example, distributed magnet 42 below sputtering target 47, and this magnet 42, shakes along target platform 43 below sputtering target 47 by omitting illustrated drive unit.Supply with nitrogen and argon gas to chamber 41, on the substrate 11 that is installed on heater 44, adopt sputtering method to form semiconductor layer.
Below method when using illustrative sputter equipment among Fig. 7, that form basalis 14a and n type contact layer 14b describe.
At first, import argon gas and nitrogen after indoor 41, the temperature of substrate 11 is warming up to about 100 ℃, when substrate 11 sides apply high frequency bias, apply power in sputtering target 47 sides that constitute by metal Ga, on one side indoor pressure is remained 0.5Pa, on one side formation is made of unadulterated GaN on substrate 11 basalis 14a.
Then, with the same condition of basalis 14a under, form the n type contact layer 14b that the GaN by doping Si constitutes.At this moment, by by the illustrated Si target radiation of the omission of ion gun in being arranged at chamber 41 ion, take out Si and be doped in the GaN from the Si target.By such operation, on resilient coating 12, form the basalis 14a that constitutes by unadulterated GaN, and then form the n type contact layer 14b that the GaN by doping Si constitutes thereon.
As the sputtering method that in the manufacture method of present embodiment, uses, preferably, sputtering target is applied power by using RF (high frequency) sputtering method or DC sputtering method.
In addition, when using reactive sputtering method described later usually, can control film forming speed easily, therefore more preferably use the RF sputtering method.
In addition, in the DC sputtering method, when using the reactive sputtering method, when when applying the state of electric field continuously with DC, the sputtering target charging is difficult to improve film forming speed, thus preferred pulse give the pulsed DC sputtering method of bias voltage.
In addition, when adopting sputtering method to form semiconductor layer (being basalis 14a and n type contact layer 14b in the present embodiment), come the method for film forming by the reactive sputtering method that the nitride raw material is circulated in reactor, can keep crystallinity well by the control reaction, and it is can stably reproduce its good crystallinity, thereby preferred.
In addition, when adopting sputtering method to form semiconductor layer, the sputter equipment of representing as Fig. 7 40 is preferably with respect to sputtering target 47 rotating magnetic fields or shake magnetic field.
When particularly using the RF sputter, as the method that obtains uniform thickness, preferred on one side at target (sputtering target) on one side in the position of shifting magnetic field carry out film forming.The movement technique of concrete magnet can suitably be selected according to the kind of sputter equipment, for example, magnet is shaken or rotatablely moves.
In addition, when using sputtering method to form the mixed crystal layer, there is the metal that will become target in advance to make the method for the mixture of metal material (can form alloy), in addition, also can be two targets that preparation is made of different materials, the method for carrying out sputter simultaneously.For example, when forming the film of definite composition, use the target of composite material, when forming different several film film forming, a plurality of targets are arranged at indoor getting final product.
When adopting sputtering method to form basalis 14a and n type contact layer 14b, the method of carrying out film forming in reactor by the reactive sputtering method that the nitride raw material is circulated can be adopted,, crystallinity can be kept well by the control reaction, can stably reproduce its good crystallinity, therefore more preferably.In addition, when adopting sputtering method to form basalis 14a and n type contact layer 14b, compare, can make device become easy formation with mocvd method, MBE method etc.
In the manufacture method of present embodiment, N 2Flow is with respect to nitrogen (N 2) and the ratio of the flow of argon (Ar) be preferably 20%～98% scope.When being the N that is lower than this scope 2During flow-rate ratio, splash-proofing sputtering metal is attached on the substrate with metallic state.In addition, when being when being higher than the flow-rate ratio of above-mentioned scope, because the amount of Ar is very few, so sputtering rate reduces.
The nitrogen flow is with respect to N 2Ratio with the flow of Ar is preferably 25%～90% scope especially.
In the manufacture method of present embodiment, as described above, make the N in the indoor gas of sputter equipment 2The concentration height, and then, with the Ar of above-mentioned flow-rate ratio mixing as the big gas of weight.When indoor gas only is N 2The time, owing to knock a little less than the power of metallic target 47, therefore limited film forming speed, in the present embodiment,, can improve film forming speed, and can make the migration on the substrate 11 active by mixing with the big Ar of above-mentioned flow-rate ratio and weight.
As the nitrogen raw material that uses in the present embodiment, can be without any restrictedly using known nitrogen compound usually, but ammonia, N 2Gas is simple to operate, and can obtain more at an easy rate, thereby preferred.
The ammonia decomposition efficiency is good, can carry out film forming with the high speed of growth, but because reactivity or toxicity height, therefore need remove the evil equipment and detector in addition, must make the material of the member that uses in the reaction unit be the high material of chemical stability.
In addition, when using nitrogen as raw material, as device can be easy to use device, but can not obtain high reaction speed.But, adopt by importing to the method in the device behind the decompositions nitrogen such as electric field or heat, can, so consider and take into account the nitrogenous source that is best suited in installation cost though obtain lowlyer but can be used for the film forming speed of industrial degree than ammonia.
In the manufacture method of present embodiment, when forming basalis 14a and n type contact layer 14b, the pressure in the chamber 41 is preferably below the 10Pa, in addition, more preferably below the 5Pa, most preferably is below the 1Pa.Pressure in the chamber 41 can form good basalis 14a of crystallinity and n type contact layer 14b with high efficiency in above-mentioned scope the time.When the pressure in the chamber 41 surpassed 10Pa, worry can not obtain good basalis 14a of crystallinity and n type contact layer 14b.
Moreover the pressure in the chamber 41 when adopting sputtering method to form semiconductor layer is preferably more than the 0.3Pa.Pressure in the chamber 41 is during less than 0.3Pa, and the amount of nitrogen becomes too small, worries to be attached on the substrate 11 with the state that does not become nitride by the metal of sputter.
The inventor etc. carry out found that of deep experiment, research, and the temperature of the substrate 11 when adopting sputtering method to form semiconductor layer is preferably 400 ℃～1300 ℃ scope.This be because, the temperature of the substrate 11 when improve forming basalis 14a and n type contact layer 14b is easy to generate the migration of atom, the cyclisation of dislocation is carried out easily.In addition, the temperature of the substrate 11 when forming basalis 14a and n type contact layer 14b must be the low temperature of temperature of decomposing than crystallization, therefore preferably less than 1300 ℃.
In addition, be to carry out sputter in the said temperature scope by the temperature that makes substrate 11, can obtain good basalis 14a of crystallinity and n type contact layer 14b.
In the manufacture method of present embodiment, the temperature of the substrate 11 when adopting sputtering method to form semiconductor layer by making is that above-mentioned scope improves substrate temperature, can will arrive the motion activation of the reactive material (from the metal of metallic target 47 taking-ups) of substrate 11 at crystal surface thus.
In addition, the manufacture method of present embodiment, the film forming speed when adopting sputtering method to form semiconductor layer is preferably 0.1～10nm/ scope of second.
During second, film-forming process becomes for a long time film forming speed less than 0.1nm/, and waste becomes big on the industrial production.In addition, film forming speed surpasses 10nm/ during second, is difficult to obtain good film.
Manufacture method according to present embodiment, by under these conditions, use sputtering method, nitrogen and argon are supplied in indoor, form the basalis 14a and the n type contact layer 14b that constitute the n type semiconductor layer 14 among the semiconductor layer 20, can generate high bias voltage or high-power reactive material, in addition, can this reactive material be supplied to the surface of resilient coating 12 with high kinergety, so on resilient coating 12, produce migration, make the dislocation cyclisation easily.Thus, constitute the basalis 14a of the n type semiconductor layer 14 of semiconductor layer 20, can former state ground inherit the crystallinity as the resilient coating 12 of column crystallization aggregate of on substrate 11 film forming.Therefore, can be formed into membrane efficiency height, productivity ratio excellence, and the III group-III nitride compound semiconductor of crystallinity excellence.
In addition, in the manufacture method of present embodiment, use sputtering method, nitrogen and argon are supplied to indoor, form basalis 14a and n type contact layer 14b, therefore compare, can improve film forming speed, can shorten film forming (manufacturing) time with mocvd method.
By shortening manufacturing time, can suppress impurity and enter indoor in the sputter equipment to Min..
(formation of n type coating)
In the present embodiment, on the n type contact layer 14b that adopts sputtering method to form, use mocvd method to form n type coating 14c.
At this moment, the substrate 11 that stacks gradually the resilient coating 12 that obtains as described above, basalis 14a, n type contact layer 14b can be imported in the MOCVD stoves, on n type contact layer 14b, form by In by known method in the past 0.1Ga 0.9The n type coating 14c that N constitutes.
(formation of luminescent layer)
On n type coating 14c, adopt mocvd method to form luminescent layer 15.
The luminescent layer as shown in Figure 1 15 of Xing Chenging has the laminated construction that starts from the GaN barrier layer and end at the GaN barrier layer in the present embodiment, alternately stacked 6 layers the barrier layer 15a that is formed by GaN and by unadulterated In 0.2Ga 0.85 layers the trap layer 15b that N constitutes and forming.
In addition, in the manufacture method of present embodiment, can adopt known in the past mocvd method to form luminescent layer 15 by using and the identical stove of MOCVD stove that in the film forming of n type coating 14c, uses.
(formation of p type coating and p type contact layer)
On luminescent layer 15, that is, on the barrier layer 15a of the superiors that become luminescent layer 15, adopt mocvd method to form the p type semiconductor layer 16 that comprises p type coating 16a and p type contact layer 16b.
In the present embodiment, at first, go up the Al that forms by doped with Mg at luminescent layer 15 (the barrier layer 15a of the superiors) 0.1Ga 0.9The p type coating 16a that N constitutes, and then form Al thereon by doped with Mg 0.02Ga 0.98The p type contact layer 16b that N constitutes.
In the manufacture method of present embodiment, can adopt known in the past mocvd method to form p type semiconductor layer 16 by using and the identical stove of MOCVD stove that in the film forming of n type coating 14c and luminescent layer 15, uses.
＜formation of light transmission positive pole 〉
By method as described above, be to be laminated with on the substrate 11 on the p type contact layer 16b of laminated semiconductor 10 of resilient coating 12 and semiconductor layer, form the light transmission positive pole 17 that constitutes by ITO.
Formation method as light transmission positive pole 17 is not particularly limited, and can adopt the customary means of knowing in the art to be provided with.In addition, its structure can comprise any structure of known structure in the past without any restrictedly using.
In addition, though the light transmission of present embodiment anodal 17 is used ITO (In 2O 3-SnO 2) form, but be not limited to this, can use for example AZO (ZnO-Al 2O 3), IZO (In 2O 3-ZnO), GZO (ZnO-Ga 2O 3) wait material to form.
In addition, behind the formation light transmission positive pole 17, implement sometimes with alloying, the transparent thermal annealing that turns to purpose, but also can not implement.
＜formation of positive pole and negative pole 〉
On the light transmission positive pole 17 that forms on the laminated semiconductor 10, further form positive terminal pad 18.
This positive terminal pad 18 for example can be utilized known method in the past, begins to stack gradually Ti, Al, each material of Au from the face side of light transmission positive pole 17 and forms.
In addition, when forming negative pole 19, at first remove the part of the p type semiconductor layer 16, luminescent layer 15 and the n type semiconductor layer 14 that form by methods such as dry ecthings on substrate 11, what form n type contact layer 14b thus exposes regional 14d (with reference to Fig. 2 and Fig. 3).
Then, expose on the regional 14d, for example adopt in the past that known method begins to stack gradually each material of Ni, Al, Ti and Au from exposing regional 14d face side, can form the negative pole 19 of 4 layers of structure at this.
Then, for the wafer that on laminated semiconductor 10, is provided with light transmission positive pole 17, positive terminal pad 18 and negative pole 19 as described above, grind the back side of cutting and grinding substrate 11, after forming specular face, for example, can be made into light-emitting element chip (light-emitting component 1) by cutting into the square square of 350 μ m.
Manufacture method according to the III group-III nitride compound semiconductor light-emitting device of present embodiment as described above adopts above-mentioned formation, can adopt sputtering method to form the crystalline film that has good uniformity with the short time.Thus, can stably form the good III group-III nitride compound semiconductor layer of crystallinity.
In the manufacture method of present embodiment, under these conditions, form to constitute the semiconductor layer 20 that forms by the III group-III nitride compound that comprises Ga layer among, when the basalis 14a of n type semiconductor layer 14 and n type contact layer 14b, in chamber 41, carry out sputter by supplying with nitrogen and argon, can generate high bias voltage or high-power reactive material, in addition, can supply with this reactive material to substrate 11 with high kinergety, therefore on resilient coating 12, move, easily with the dislocation cyclisation.Thus, the basalis 14a of n type semiconductor layer 14, can former state ground inherit the crystallinity as the resilient coating 12 of the aggregate of column crystallization of on substrate 11 film forming.Thus, can form the good semiconductor layer that constitutes by III group-III nitride compound of crystallinity.
In addition, in the present embodiment, as described above, carry out sputter by supply nitrogen and argon in chamber 41, and form basalis 14a and n type contact layer 14b, therefore can improve the film forming speed of semiconductor layer 20, can shorten film forming (manufacturing) time.And then by shortening manufacturing time, the indoor situation that impurity can be entered in the sputter equipment suppresses to be Min..
Thereby, the III group-III nitride compound semiconductor light-emitting device that can obtain the productivity ratio excellence and have the excellent characteristics of luminescence.
[lamp]
Constitute lamp by making up III group-III nitride compound semiconductor light-emitting device of the present invention and fluorophor as described above, can utilize the means that well known to a person skilled in the art.All the time, known have a technology that changes illuminant colour by illuminated in combination element and fluorophor, can be without any restrictedly adopting such technology.
For example,, can obtain the luminous of the wavelength longer, in addition,, can be made into the alight that is white in color by the emission wavelength of mixed luminescence element self and the wavelength of changing by fluorophor than light-emitting component by suitably selecting fluorophor.
In addition, as lamp, can be used for any purposes of lateral emitting (side view) type of general purpose bullet cut, portable purposes backlight, top light emitting (top view) type that in display, uses etc.
For example, as the example that Fig. 4 represents, in the time of will being mounted to bullet cut with the III group-III nitride compound semiconductor light-emitting device 1 of an electrode type, one (being frame 31 in Fig. 4) in two frames gone up bonding light-emitting component 1, in addition, with line 34 negative pole of light-emitting component 1 (symbol of representing with reference to Fig. 3 19) is engaged with frame 32, the positive terminal pad of light-emitting component 1 (symbol of representing with reference to Fig. 3 18) is engaged with frame 31 with line 33.Then, the periphery of light-emitting component 1 is carried out molding, make the lamp 3 of bullet cut shown in Figure 4 by the mold 35 that constitutes by transparent resin.
In addition, III group-III nitride compound semiconductor light-emitting device of the present invention except above-mentioned light-emitting component, also can be used for the photo-electric conversion element of laser diode and photo detector etc. or the electronic device of HBT, HEMT etc. etc.These semiconductor elements, the known semiconductor element that a lot of various structures are arranged, the component structure of the laminated structure of III group-III nitride compound semiconductor light-emitting device of the present invention comprises these known elements structures and without any restriction.
Then, illustrate in greater detail the manufacture method of III group-III nitride compound semiconductor light-emitting device of the present invention by embodiment, but the present invention is not limited in these embodiment.
[embodiment 6]
Fig. 1 represents the cross section ideograph of the laminated semiconductor of the III group-III nitride compound semiconductor light-emitting device that this experimental example is made.
In this example, on the c face of the substrate 11 that constitutes by sapphire, as resilient coating 12, use the RF sputtering method to form the aggregate of the column crystallization that constitutes by AlN, as basalis 14a and n type contact layer 14b, use the RF sputtering method to form the layer that constitutes by GaN thereon.
At first, by only one side being carried out the substrate 11 that mirror ultrafinish to the sapphire that can be used for epitaxially grown degree constitutes, do not carry out the pre-treatment of wet type particularly etc. and import in the sputter equipment.Here,, used to have the high frequency type power supply as sputter equipment, and have can be in target the device of the mechanism of the position of moving magnet.
Then, in sputter equipment, substrate 11 is heated to 750 ℃, only import nitrogen with the flow of 15sccm after, indoor pressure is remained on 0.08Pa, apply the high frequency bias of 50W in substrate 11 sides, be exposed in the nitrogen plasma, wash substrate 11 surfaces thus.
Then, after in sputter equipment, importing argon and nitrogen, make the temperature of substrate 11 be reduced to 500 ℃.Then, apply 0.5W/cm in substrate 11 sides 2High frequency bias the time, apply 1W/cm in metal A l target side 2Power, keeping the pressure in the stove is 0.5Pa, under with 5sccm circulation argon gas, condition with 15sccm circulation nitrogen (ratio of nitrogen in gas is all is 75%), forms the resilient coating 12 that is made of AlN on the substrate 11 that is made of sapphire.
Magnet in the time of washing arbitrary during substrate 11 and during film forming in the rotary target.
Then, carry out the processing of stipulated time, behind the AlN film (resilient coating 12) of formation 50nm, stop plasma work, reduce the temperature of substrate 11 according to the film forming speed of measuring in advance (0.12nm/ second).
Then, from sputter equipment, take out the substrate 11 that has formed resilient coating 12, be transported in the other sputter equipment, use sputtering method to form the sample of GaN layer (III group-III nitride semiconductor) according to following sequentially built.Here,, use to have high-frequency power supply, and have by magnet and scan in the dimetric Ga target device of the mechanism of the position that removable magnetic field applies as the sputter equipment that forms the GaN layer.In addition, the pipe arrangement of the refrigerant that is provided for circulating in the Ga target circulates the refrigerant that is cooled to 20 ℃ in pipe arrangement, prevents the fusing of the Ga that caused by heat.
At first, behind indoor importing argon gas and nitrogen, the temperature of substrate 11 is warming up to 1000 ℃.Then, apply 0.5W/cm in substrate 11 sides 2High frequency bias, simultaneously apply 1W/cm in metal Ga target side 2Power, when the pressure in the holding chamber was 0.5Pa, (all ratios of nitrogen and gas are 75%) formed the layer (basalis 14a) that is made of GaN on substrate 11 under with 5sccm circulation argon gas, condition with 15sccm circulation nitrogen.The speed of growth of this moment is approximately 1nm/ second.Then, form the GaN layer of 6 μ m after, stop to produce plasma.
Then, under same condition, formation has 1 * 10 19Cm -3The GaN layer (n type contact layer 14b) of doping Si of 2 μ m of electron concentration.Each condition of film forming and unadulterated GaN layer are same, to being arranged at the ion that indoor Si target radiation emitted by ion gun and taking out Si, thus doping Si.
By above operation, on the substrate 11 that constitutes by sapphire, form the resilient coating 12 that has column structure and constitute by AlN, form the GaN layer (basalis 14a) of the thickness of 6 μ m thereon with unadulterated form, formation has 1 * 10 thereon again 19Cm -3The GaN layer (n type contact layer 14b) of doping Si of 2 μ m of electron concentration, made the sample of embodiment 6.This specimen surface presents water white specular.
Then, use X ray analyzer (パ Na リ テ イ カ Le society system; Four crystallization X ray determinators, model: X ' pert) measure the X ray swing curve (XRC) of the unadulterated GaN layer (basalis 14a) that obtains by said method.This measure to use Cu β ray X ray the source to take place as light source, is carrying out as (0002) face of the plane of symmetry with as (10-10) face of asymmetric.Usually, under the situation of III group-III nitride compound semiconductor, the wide index that becomes the flatness (モ ザ イ シ テ イ) of crystallization of the XRC spectrum half value of (0002) face, (10-10) wide dislocation density (helical form that becomes of the XRC spectrum half value of face; Twist) index.The result of this mensuration, the unadulterated GaN layer that utilizes manufacture method of the present invention to make shows the wide 80arcsec of half value in the mensuration of (0002) face, show the wide 250arcsec of half value for (11-20) face.
[embodiment 7]
In this example, in the unadulterated GaN crystallization (basalis 14a) of 6 μ m of film forming under the condition similarly to Example 6, use identical sputter equipment, formed the n type contact layer 14b of doping Si.
Then, sample is imported in the MOCVD stove, form each layer on it, finally made the epitaxial wafer with epitaxial layer structure (laminated semiconductor 10) that III group-III nitride compound semiconductor light-emitting device is as shown in Figure 1 used.
This epitaxial wafer has following structure: on the substrate 11 that is made of the sapphire with c face, by growing method similarly to Example 1, formation begins sequentially stacked from substrate 11 sides after having the resilient coating 12 that is made of AlN of column structure: the basalis 14a that is formed by unadulterated GaN of 6 μ m, by having 1 * 10 19Cm -3The n type contact layer 14b that constitutes of the GaN of 2 μ m of electron concentration by doping Si, have 1 * 10 18Cm -3The In of 20nm of electron concentration 0.1Ga 0.9N type coating (n type coating 14c), start from the GaN barrier layer and end at the GaN barrier layer laminated construction, alternately to be laminated with bed thickness be the unadulterated In that 6 layers barrier layer 15a constituting of the GaN of 16nm and bed thickness are 3nm 0.2Ga 0.8The luminescent layer (multi-quantum pit structure) 15 that 5 layers the trap layer 15b that N constitutes forms, Al by doped with Mg with 5nm 0.1Ga 0.9 P type coating 16a that N constitutes and the Al of thickness 200nm by doped with Mg 0.02Ga 0.98The p type semiconductor layer 16 of the p type contact layer 16b that N constitutes.
By above order, made the epitaxial wafer that semiconductor light-emitting elements is used with epitaxial layer structure.Here, by the Al of doped with Mg 0.02Ga 0.98The p type contact layer 16b that N constitutes even be not used for annealing in process with p type carrier activation, also demonstrates p type characteristic.
Then, use the epitaxial wafer that on the substrate 11 that constitutes by sapphire, is laminated with epitaxial layer structure (with reference to the laminated semiconductor 10 of Fig. 1) as described above, make a kind of light-emitting diode (with reference to the light-emitting component 1 of Fig. 2 and Fig. 3) as semiconductor light-emitting elements.
At first, for the wafer of making, by known photoetching process at Al by doped with Mg 0.02Ga 0.98On the surface of the p type contact layer 16b that N constitutes, form the light transmission positive pole 17 that constitutes by ITO and have thereon from the anodal face side positive terminal pad 18 of structure of Ti, Al, Au that begun sequential cascade.In addition, the part of wafer is implemented dry ecthing, expose the regional 14d that exposes on the n type contact layer 14b, on this part, make by these 4 layers of negative poles that constitutes 19 of Ni, Al, Ti and Au.By these operations, on wafer, made each electrode with shape of representing as Fig. 2 and Fig. 3.
For this has formed the wafer of electrode on two-layer in p type semiconductor layer and n type semiconductor layer as described above, grind the dorsal part of cutting and grind substrate 11, make specular face, cut into the square foursquare chip of 350 μ m, each electrode up mounting on lead frame, by being connected in lead frame, made semiconductor light-emitting elements with gold thread.The forward current that circulates between the electrode of the positive terminal pad 18 of this semiconductor light-emitting elements (light-emitting diode) and negative pole 19, the forward voltage under the electric current 20mA is 3.0V.In addition, observe luminance by the light transmission anodal 17 of p side, emission wavelength is 470nm, and luminous power output shows 15mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of the roughly whole making of the wafer of making, does not obtain with can having deviation.
In addition, in embodiment 7, the required time of whole operations that above-mentioned film forming is handled is 8 hours.
[comparative example 1]
In this example, on the c of the substrate that constitutes by sapphire face,, use the RF sputter equipment of rotating cathode formula as resilient coating, and to make substrate temperature be 700 ℃, forming the aggregate of the column crystallization of AlN, in addition, only is nitrogen to indoor gas supplied, and make substrate temperature be 900 ℃ and form basalis, in addition, with the same condition of embodiment 6 and embodiment 7 under, form basalis 14a and n type contact layer 14b by sputter.Then, from reaction unit, take out wafer, but the surface of Visual Confirmation wafer is a minute surface.
Then, on said n type contact layer 14b, adopt mocvd method to form the light-emitting component semiconductor laminated structure similarly to Example 7.
Then, with the wafer of making as described above, make light-emitting diode chip for backlight unit similarly to Example 2.The forward current that circulates between electrode, the forward voltage under the electric current 20mA is 3.5V.In addition, luminous by the anodal observation of the light transmission of p side, emission wavelength is 470nm, and luminous power output shows 9mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of roughly making of the wafer of making comprehensively, does not obtain with can having deviation.
But, in comparative example 1, can confirm that film forming speed is about 1/3 the speed of embodiment 6.In addition, in comparative example 1, the needed time of whole operations that film forming is handled is 14 hours, and it is elongated that result and embodiment 7 compare activity time.
[comparative example 2]
In this example, except the room pressure that makes sputter equipment is 15Pa, similarly operate, on resilient coating 12, adopt sputtering method to form basalis 14a and n type contact layer 14b with embodiment 6 and embodiment 7.Then, take out wafer from reaction unit, the surface haze of wafer can not film forming form light emitting element structure.
[comparative example 3]
In this example, except the temperature that makes substrate 11 is 200 ℃, similarly operate, on resilient coating 12, adopt sputtering method to form basalis 14a and n type contact layer 14b with embodiment 6 and embodiment 7.Then, take out wafer from reaction unit, the surface haze of wafer can not film forming form light emitting element structure.
[comparative example 4]
In this example, be 20nm/ second except making film forming speed, similarly operate with embodiment 6 and embodiment 7, on resilient coating 12, adopt sputtering method to form basalis 14a and n type contact layer 14b.Then, take out wafer from reaction unit, the surface haze of wafer can not film forming form light emitting element structure.
[embodiment 8]
In this example, on ZnO (0001) substrate, as resilient coating, use the RF magnetron sputtering method to form the aggregate of the column crystallization of GaN,, use the device identical thereon, the basalis that formation is made of the AlGaN of doped with Ge with embodiment 6, on basalis, form the n type contact layer that the AlGaN by doping Si constitutes.Then, and then adopt similarly to Example 7 method thereon, form the light-emitting component semiconductor laminated structure by mocvd method.Here, the Al of basalis consists of 10%.In addition, the temperature of the substrate when carrying out the sputter of resilient coating is a room temperature, and the temperature of the substrate when carrying out the film forming of basalis is 750 ℃.In addition, in this example,, increase the material flow of the In that contains in the luminescent layer in order to attempt making near the green LED the 525nm.
In embodiment 8, grow the light-emitting component semiconductor laminated structure after, from reaction unit, take out wafer, the surface that can confirm wafer is a minute surface.
With the wafer of making as described above, adopt method similarly to Example 7 to make light-emitting diode chip for backlight unit, then, the forward current that circulates between electrode, the forward voltage under the electric current 20mA are 3.0V.In addition, luminous by the anodal observation of the light transmission of p side, emission wavelength is 525nm, and luminous power output shows 8mW.The characteristics of luminescence of such light-emitting diode for for the light-emitting diode of roughly making of the wafer of making comprehensively, does not obtain with can having deviation.
By above result as can be known, III group-III nitride compound semiconductor light-emitting device of the present invention, the productivity ratio excellence, and have the excellent characteristics of luminescence.
Utilize possibility on the industry
By the III iii-v nitride compound semiconductor light-emitting elements that the present invention obtains, have by having good The superficial layer that crystalline III iii-v nitride compound semiconducting crystal consists of.
Therefore, can make light emitting diode, laser diode or the electronics with excellent characteristics of luminescence The semiconductor element of device etc.
Among the present invention the expression number range " more than " and " following " include given figure.

Claims (53)

1. the manufacture method of an III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, in with described substrate and the configuration of sputtering target subtend ground, make the scope that is spaced apart 20～100mm of described substrate and described sputtering target.
2. the manufacture method of an III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when forming described semiconductor layer, the power that puts on sputtering target applies by high-frequency mode or pulsed D C mode.
3. the manufacture method of an III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when forming described semiconductor layer, making the indoor vacuum degree of using in sputter in advance is 1.0 * 10 -3After Pa is following, to described indoor base feed.
4. the manufacture method of an III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that making the pass, position of described substrate and sputtering target is in the face of formula.
5. the manufacture method of an III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when forming described semiconductor layer, make the magnetic field rotation or magnetic field is shaken with respect to sputtering target.
6. according to the manufacture method of each described III group-III nitride compound semiconductor light-emitting device of claim 1～5, it is characterized in that, form described semiconductor layer in reactor by the reactive sputtering method that the nitride raw material is circulated.
7. the manufacture method of III group-III nitride compound semiconductor light-emitting device according to claim 6 is characterized in that, uses nitrogen as described nitride raw material.
8. according to the manufacture method of each described III group-III nitride compound semiconductor light-emitting device of claim 1～7, it is characterized in that, between described substrate and described semiconductor layer, form the resilient coating that comprises column crystallization.
9. the manufacture method of III group-III nitride compound semiconductor light-emitting device according to claim 8 is characterized in that, adopts sputtering method to form described resilient coating.
10. according to Claim 8 or the manufacture method of 9 described III group-III nitride compound semiconductor light-emitting devices, it is characterized in that, form described resilient coating by the III group-III nitride compound that contains as the Al of III family element.
11. the manufacture method of III group-III nitride compound semiconductor light-emitting device according to claim 10 is characterized in that, forms described resilient coating by AlN.
12. the manufacture method of the described III group-III nitride of according to Claim 8～11 each compound semiconductor light-emitting device is characterized in that, forms described resilient coating in the mode more than at least 90% on the surface that covers described substrate.
13. the manufacture method of the described III group-III nitride of according to Claim 8～12 each compound semiconductor light-emitting device is characterized in that the width that constitutes the column crystallization of described resilient coating is the scope of 0.1～100nm.
14. the manufacture method of the described III group-III nitride of according to Claim 8～13 each compound semiconductor light-emitting device is characterized in that the thickness of described resilient coating is the scope of 10～500nm.
15. the manufacture method of the described III group-III nitride of according to Claim 8～14 each compound semiconductor light-emitting device, it is characterized in that, when forming described resilient coating, form the described semiconductor layer that forms by III group-III nitride compound by GaN by AlN.
16. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 1～15 is characterized in that, described substrate uses sapphire.
17. an III group-III nitride compound semiconductor light-emitting device, it is to adopt each described manufacture method of claim 1～16 to obtain.
18. a lamp, it has used the described III group-III nitride of claim 17 compound semiconductor light-emitting device.
19. the manufacture method of an III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when adopting sputtering method to form described semiconductor layer, making the bias value that puts on described substrate is 0.1W/cm 2More than.
20. the manufacture method of an III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when adopting sputtering method to form described semiconductor layer, making the power that puts on sputtering target is 0.1W/cm 2～100W/cm 2Scope.
21. the manufacture method according to claim claim 19 or 20 described III group-III nitride compound semiconductor light-emitting devices is characterized in that, forms described semiconductor layer by the reactive sputtering method that the nitride raw material is circulated in reactor.
22. the manufacture method of III group-III nitride compound semiconductor light-emitting device according to claim 21 is characterized in that, has used nitrogen as described nitride raw material.
23. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 19～22 is characterized in that, forms the resilient coating that comprises column crystallization between described substrate and described semiconductor layer.
24. the manufacture method of III group-III nitride compound semiconductor light-emitting device according to claim 23 is characterized in that, adopts sputtering method to form described resilient coating.
25. the manufacture method according to claim 23 or 24 described III group-III nitride compound semiconductor light-emitting devices is characterized in that, forms described resilient coating by the III group-III nitride compound that contains Al.
26. the manufacture method of III group-III nitride compound semiconductor light-emitting device according to claim 25 is characterized in that, forms described resilient coating by AlN.
27. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 23～26 is characterized in that, forms described resilient coating in the mode more than at least 90% on the surface that covers described substrate.
28. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 23～27 is characterized in that the width that constitutes the column crystallization of described resilient coating is the scope of 0.1～100nm.
29. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 23～28 is characterized in that the thickness of described resilient coating is the scope of 10～500nm.
30. manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 23～29, it is characterized in that, when forming described resilient coating, form the described semiconductor layer that forms by III group-III nitride compound by GaN by AlN.
31. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 19～30 is characterized in that, described substrate uses sapphire.
32. an III group-III nitride compound semiconductor light-emitting device, it is to adopt each described manufacture method of claim 19～32 to obtain.
33. a lamp, it has used the described III group-III nitride of claim 32 compound semiconductor light-emitting device.
34. the manufacture method of an III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when forming described semiconductor layer, thereby carry out sputter to the indoor supply nitrogen and the argon that in sputter, use.
35. the manufacture method of an III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that, when forming described semiconductor layer, make the indoor pressure that in sputter, uses as below the 10Pa.
36. the manufacture method of an III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that the temperature of the described substrate when forming described semiconductor layer is 400 ℃～1300 ℃ a scope.
37. the manufacture method of an III group-III nitride compound semiconductor light-emitting device, it is the manufacture method that comprises the III group-III nitride compound semiconductor light-emitting device of the operation that adopts sputtering method on substrate, to form the semiconductor layer that constitutes by the III group-III nitride compound semiconductor that contains as the Ga of III family element, it is characterized in that the film forming speed when forming described semiconductor layer is 0.1～10nm/ scope of second.
38. manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 34～37, it is characterized in that, on described substrate,, stack gradually each layer of n type semiconductor layer, luminescent layer, p type semiconductor layer at least and film forming as described semiconductor layer.
39. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 34～38 is characterized in that, forms described semiconductor layer by the reactive sputtering method that the nitride raw material is circulated in reactor.
40. the manufacture method according to the described III group-III nitride of claim 39 compound semiconductor light-emitting device is characterized in that, as described nitride raw material, uses nitrogen.
41. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 34～40 is characterized in that, forms the resilient coating that comprises column crystallization between described substrate and described semiconductor layer.
42. the manufacture method according to the described III group-III nitride of claim 41 compound semiconductor light-emitting device is characterized in that, adopts sputtering method to form described resilient coating.
43. the manufacture method according to claim 41 or 42 described III group-III nitride compound semiconductor light-emitting devices is characterized in that, forms described resilient coating by the III group-III nitride compound that contains as the Al of III family element.
44. the manufacture method according to the described III group-III nitride of claim 43 compound semiconductor light-emitting device is characterized in that, forms described resilient coating by AlN.
45. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 41～44 is characterized in that, forms described resilient coating in the mode more than at least 90% on the surface that covers described substrate.
46. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 41～45 is characterized in that the width that constitutes the column crystallization of described resilient coating is the scope of 0.1～100nm.
47. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 41～46 is characterized in that the thickness of described resilient coating is the scope of 10～500nm.
48. manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 41～47, it is characterized in that, when forming described resilient coating, form the described semiconductor layer that forms by III group-III nitride compound by GaN by AlN.
49. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 41～48 is characterized in that, is forming the basalis that has in described n type semiconductor layer on the described resilient coating stackedly.
50. the manufacture method according to the described III group-III nitride of claim 49 compound semiconductor light-emitting device is characterized in that, the thickness of described basalis is more than the 0.1 μ m.
51. the manufacture method according to each described III group-III nitride compound semiconductor light-emitting device of claim 34～50 is characterized in that, described substrate uses sapphire.
52. an III group-III nitride compound semiconductor light-emitting device, it is to adopt each described manufacture method of claim 34～51 to obtain.
53. a lamp, it has used the described III group-III nitride of claim 52 compound semiconductor light-emitting device.
CN200780030345XA 2006-08-18 2007-08-15 Method for manufacturing group III nitride compound semiconductor light-emitting device, group III nitride compound semiconductor light-emitting device, and lamp Active CN101506946B (en)

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JP2006291082A JP2008106316A (en) 2006-10-26 2006-10-26 Method for manufacturing group iii nitride compound semiconductor light-emitting device, group iii nitride compound semiconductor light-emitting device, and lamp
PCT/JP2007/065902 WO2008020599A1 (en) 2006-08-18 2007-08-15 Method for manufacturing group iii nitride compound semiconductor light-emitting device, group iii nitride compound semiconductor light-emitting device, and lamp

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