CN101542756A - Method for manufacturing group iii nitride semiconductor light-emitting device, group iii nitride semiconductor light-emitting device, and lamp - Google Patents

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

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CN101542756A
CN101542756A CN 200780044018 CN200780044018A CN101542756A CN 101542756 A CN101542756 A CN 101542756A CN 200780044018 CN200780044018 CN 200780044018 CN 200780044018 A CN200780044018 A CN 200780044018A CN 101542756 A CN101542756 A CN 101542756A
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iii nitride
nitride semiconductor
intermediate layer
iii
emitting component
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横山泰典
三木久幸
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Resonac Holdings Corp
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Showa Denko KK
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Abstract

The present invention is to provide a manufacturing method of a group III nitride compound semiconductor light-emitting element for producing an element that has superior light emission characteristics, while exhibiting superior productivity, and to provide the group III nitride compound semiconductor light-emitting element and a lamp. According to the method, an intermediate layer 12 comprising a group III nitride compound is formed on a substrate 11, by activating a metal material and gas containing a group V element by plasma and causing reaction, and an n-type semiconductor layer 14 comprising a group III nitride compound semiconductor, a light-emitting layer 15, and a p-type semiconductor layer 16 are sequentially laminated on the intermediate layer 12; and in this manufacturing method, the group V element is nitride and the molar fraction of nitrogen gas in the gas is set to be in a range of 20-99%, when the intermediate layer 12 is formed.

Description

The manufacture method of III group-III nitride semiconductor light-emitting component, III group-III nitride semiconductor light-emitting component and lamp
Technical field
The present invention relates to be used for manufacture method and the III group-III nitride semiconductor light-emitting component and the lamp of the III group-III nitride semiconductor light-emitting component of light-emitting diode (LED), laser diode (LD), electronic device etc. with being well suited for.
The application based on December 20th, 2006 at patent application 2006-343019 number of Japanese publication with require priority patent application 2007-214539 number of Japanese publication on August 21st, 2007, the content of above-mentioned these applications is quoted wherein.
Background technology
III group-III nitride semiconductor light-emitting component has the band gap of the Direct Transfer type of the energy that is equivalent to the scope from the visible light to the ultraviolet region, the luminous efficiency excellence, and therefore the light-emitting component as LED, LD etc. uses.
In addition, even be used for the occasion of electronic device, the III group-III nitride semiconductor is compared with the situation of using existing III-V compound semiconductor, also can access the electronic device with excellent specific property.
In the past, as the single-chip of III group-III nitride semiconductor, generally be to make growth crystallization on the single-chip of different materials and the method that obtains.Between such dissimilar substrate and the crystallization of epitaxially grown III group-III nitride semiconductor, there is big lattice mismatch thereon.For example, make gallium nitride (GaN) at sapphire (Al 2O 3) occasion of growing on the substrate, there is 16% lattice mismatch between, the occasion that gallium nitride is grown on the SiC substrate, and there is 6% lattice mismatch between.
Usually, there is the occasion of aforesaid bigger lattice mismatch, is difficult to make crystallization directly epitaxial growth on substrate, and, even also there is the problem that can not obtain the good crystallization of crystallinity in the occasion of having grown.
Therefore, once having proposed employing metal organic chemical vapor deposition (MOCVD) method makes the crystallization of III group-III nitride semiconductor on sapphire single crystal substrate or SiC monocrystal substrate during epitaxial growth, the at first stacked layer that is called low temperature buffer layer that forms by aluminium nitride (AlN), aluminium gallium nitride alloy (AlGaN) on substrate, the method of epitaxial growth III group-III nitride semiconductor crystallization at high temperature thereon again, this method is carried out (for example, patent documentation 1,2) usually
In addition, also proposed to adopt MOCVD method in addition above-mentioned resilient coating to be carried out the technology of film forming.For example, propose employing sputtering method film forming on substrate and gone out resilient coating, use sapphire, silicon, carborundum, zinc oxide, gallium phosphide, GaAs, magnesium oxide as baseplate material simultaneously, the method of manganese oxide and III group-III nitride based compound semiconductor monocrystalline etc., wherein, sapphire a face substrate is well suited for (for example, patent documentation 3,4).
Yet, patent documentation 1～4 described method, existence can not obtain the problem of sufficient crystalline III group-III nitride semiconductor.
On the other hand, once proposed to adopt MOCVD on resilient coating, to grow the method (for example, patent documentation 5) of the crystallization of same composition by the high-frequency sputtering film forming.Yet, patent documentation 5 described methods, the problem of can not be on the substrate stably stacked good crystallization of existence.
In addition, when also having proposed the employing sputtering method forming resilient coating on substrate, the initial stage voltage that makes sputter equipment is the method below 110% (for example, patent documentation 6) of sputtering voltage.Patent documentation 6 described methods are the materials that do not use as the employed high price of mocvd method, and adopt sputtering method to form the method for resilient coating.
Patent documentation 1: No. 3026087 communique of Japan Patent
Patent documentation 2: Japanese kokai publication hei 4-297023 communique
Patent documentation 3: No. 3440873 communique of Japan Patent
Patent documentation 4: No. 3700492 communique of Japan Patent
Patent documentation 5: the special fair 5-86646 communique of Japan
Patent documentation 6: TOHKEMY 2001-308010 communique
Summary of the invention
After above-mentioned patent documentation 3 described methods are buffer growth, the method for in the gaseous mixture that comprises ammonia and hydrogen, annealing.In addition, patent documentation 4 described methods importantly adopt DC to sputter at that film forming goes out resilient coating under the temperature more than 400 ℃.Yet the result that present inventors experimentize with great concentration clear and definite can not obtain good crystalline III group-III nitride semiconductor under patent documentation 3,4 described conditions.
At this, patent documentation 1,2 described mocvd methods, be to make unstripped gas reach the temperature more than the decomposition temperature of this unstripped gas and decompose, the method that consequent analyte is grown on template, though it is the speed of growth is low, known as the method that can obtain the high film of crystallinity.
On the other hand, but think that sputtering method is to pound atom from target, the method for the atom film forming on substrate that forcibly this quilt is pounded, though fast growth, the film that obtains is compared crystallinity with mocvd method not high.For this reason, mainly adopted in the past mocvd method on the substrate with the resilient coating film forming after, the GaN layer of the non-doping by growing several μ m on this film improves the crystalline method of the luminescent layer of growing on this film.
Yet, adopt the method that forms resilient coating as above-mentioned mocvd method, can not obtain sufficient crystallinity, therefore expectation can obtain the method for the good film of crystallinity.
The present invention is the research of finishing in view of above-mentioned problem, its purpose is to provide the III group-III nitride semiconductor that can grow excellent in uniformity in the short time on substrate, the productivity ratio excellence, the while can access manufacture method and the III group-III nitride semiconductor light-emitting component and the lamp of the III group-III nitride semiconductor light-emitting component of the element with excellent characteristics of luminescence.
Present inventors are in order to address the above problem found that of studying with great concentration, film forming speed is compared in employing with mocvd method very high, and forcibly on substrate the sputtering method of film forming etc. by the method for plasma with the raw material activation, film forming goes out intermediate layer (resilient coating), and, making the dividing potential drop as the nitrogen raw material of V group element is optimum range, thus can be as the film forming on substrate of the alignment films with specific anisotropy, film forming speed improves simultaneously, the impurity that can prevent attachment in the stove etc. is sneaked in the film, thereby has finished the present invention.
That is, the present invention relates to following invention.
[1] a kind of manufacture method of III group-III nitride semiconductor light-emitting component, be to make its reaction by the gas and the metal material activation that will contain V group element by plasma, thereby film forming goes out the intermediate layer that is formed by III group-III nitride compound on substrate, on this intermediate layer, stack gradually the n type semiconductor layer that forms by the III group-III nitride semiconductor, the manufacture method of the III group-III nitride semiconductor light-emitting component of luminescent layer and p type semiconductor layer, it is characterized in that, above-mentioned V group element is a nitrogen, the gas branch rate of the nitrogen in the above-mentioned gas when forming above-mentioned intermediate layer is greater than 20% and in the scope below 99%, and forms above-mentioned intermediate layer as single crystal organization.
According to the manufacture method of [1] described III group-III nitride semiconductor light-emitting component, it is characterized in that [2] the gas branch rate of the nitrogen in the above-mentioned gas when forming above-mentioned intermediate layer is greater than 40% and in the scope below 99%.
According to the manufacture method of [1] described III group-III nitride semiconductor light-emitting component, it is characterized in that [3] the gas branch rate of the nitrogen in the above-mentioned gas when forming above-mentioned intermediate layer is greater than 75% and in the scope below 99%.
[4] manufacture method of each described III group-III nitride semiconductor light-emitting component of basis [1]～[3] is characterized in that, adopts sputtering method to form above-mentioned intermediate layer.
[5] according to the manufacture method of [4] described III group-III nitride semiconductor light-emitting component, it is characterized in that, adopt the RF sputtering method to form above-mentioned intermediate layer.
[6] according to the manufacture method of [5] described III group-III nitride semiconductor light-emitting component, it is characterized in that, form above-mentioned intermediate layer while adopt the RF sputtering method that the magnet of negative electrode is moved.
[7] according to the manufacture method of each described III group-III nitride semiconductor light-emitting component of [4]～[6], it is characterized in that, adopt the reactive sputtering that the gas that contains V group element is circulated in reactor to form above-mentioned intermediate layer.
[8] manufacture method of each described III group-III nitride semiconductor light-emitting component of basis [1]～[7] is characterized in that above-mentioned metal material is the material that contains Al.
The manufacture method of the described III group-III nitride semiconductor light-emitting component of each of [9] [1]～[8] is characterized in that, forms above-mentioned intermediate layer by AlN.
According to the manufacture method of each described III group-III nitride semiconductor light-emitting component of [1]～[9], it is characterized in that [10] temperature that makes aforesaid substrate is that the scope of room temperature～1000 ℃ forms above-mentioned intermediate layer.
[11] manufacture method of each described III group-III nitride semiconductor light-emitting component of basis [1]～[9] is characterized in that the temperature that makes aforesaid substrate is that 200～800 ℃ scope forms above-mentioned intermediate layer.
[12] manufacture method of each described III group-III nitride semiconductor light-emitting component of basis [1]～[11] is characterized in that the basalis that stacked said n type semiconductor layer is had on above-mentioned intermediate layer.
[13] according to the manufacture method of [12] described III group-III nitride semiconductor light-emitting component, it is characterized in that, form above-mentioned basalis by the GaN based compound semiconductor.
[14] according to the manufacture method of [13] described III group-III nitride semiconductor light-emitting component, it is characterized in that, form above-mentioned basalis by GaN.
[15] according to the manufacture method of [13] described III group-III nitride semiconductor light-emitting component, it is characterized in that, form above-mentioned basalis by AlGaN.
[16] manufacture method of each described III group-III nitride semiconductor light-emitting component of basis [12]～[15] is characterized in that, forms above-mentioned intermediate layer and above-mentioned basalis respectively by different III group-III nitride compounds.
[17] manufacture method of each described III group-III nitride semiconductor light-emitting component of basis [12]～[16] is characterized in that, adopts mocvd method to form above-mentioned basalis on above-mentioned intermediate layer.
According to the manufacture method of each described III group-III nitride semiconductor light-emitting component of [12]～[17], it is characterized in that [18] making the temperature of the aforesaid substrate when forming above-mentioned basalis is more than 800 ℃.
[19] a kind of III group-III nitride semiconductor light-emitting component is to adopt each described manufacture method of above-mentioned [1]～[18] to obtain.
[20] a kind of III group-III nitride semiconductor light-emitting component, be to react by the gas and the metal material activation that will contain V group element by plasma, thereby film forming goes out the intermediate layer that is formed by III group-III nitride compound on substrate, on this intermediate layer, stack gradually the n type semiconductor layer that forms by the III group-III nitride semiconductor, the III group-III nitride semiconductor light-emitting component that luminescent layer and p type semiconductor layer form, it is characterized in that, above-mentioned intermediate layer is that to make above-mentioned V group element be nitrogen, the gas branch rate that makes the nitrogen in the above-mentioned gas is for greater than 20% and the layer that goes out in the scope film forming below 99%, and is single crystal organization.
[21] according to [20] described III group-III nitride semiconductor light-emitting component, it is characterized in that, the gas branch rate that above-mentioned intermediate layer is that to make above-mentioned V group element be nitrogen, make the nitrogen in the above-mentioned gas for greater than 40% and the scope film forming 99% below go out layer.
[22] according to [20] described III group-III nitride semiconductor light-emitting component, it is characterized in that, above-mentioned intermediate layer be that to make above-mentioned V group element be nitrogen and the gas branch rate that makes the nitrogen in the above-mentioned gas for greater than 75% and the scope film forming 99% below go out layer.
[23] according to each described III group-III nitride semiconductor light-emitting component of [20]～[22], it is characterized in that above-mentioned intermediate layer is the composition that contains Al.
[24] according to [23] described III group-III nitride semiconductor light-emitting component, it is characterized in that above-mentioned intermediate layer is formed by AlN.
According to each described III group-III nitride semiconductor light-emitting component of [20]～[24], it is characterized in that [25] above-mentioned intermediate layer forms in the mode more than 90% that covers the aforesaid substrate surface at least.
According to each described III group-III nitride semiconductor light-emitting components of [20]～[25], it is characterized in that [26] above-mentioned intermediate layer forms in the mode of the side that covers aforesaid substrate at least.
According to each described III group-III nitride semiconductor light-emitting component of [20]～[26], it is characterized in that [27] above-mentioned intermediate layer forms with the side of covering aforesaid substrate and the mode at the back side.
[28] according to each described III group-III nitride semiconductor light-emitting component of [20]～[27], it is characterized in that above-mentioned intermediate layer is by crystal formation.
[29] according to each described III group-III nitride semiconductor light-emitting component of [20]～[28], it is characterized in that the thickness in above-mentioned intermediate layer is the scope of 20～80nm.
[30] according to each described III group-III nitride semiconductor light-emitting component of [20]～[29], it is characterized in that the basalis that the said n type semiconductor layer is had is stacked on above-mentioned intermediate layer.
[31] according to [30] described III group-III nitride semiconductor light-emitting component, it is characterized in that above-mentioned basalis is formed by the GaN based compound semiconductor.
[32] according to [31] described III group-III nitride semiconductor light-emitting component, it is characterized in that above-mentioned basalis is formed by GaN.
[33] according to [31] described III group-III nitride semiconductor light-emitting component, it is characterized in that above-mentioned basalis is formed by AlGaN.
[34] a kind of lamp, it has used each described III group-III nitride semiconductor light-emitting component of above-mentioned [19]～[33].
The invention effect
The manufacture method of root a tree name III group-III nitride semiconductor of the present invention light-emitting component, according to above-mentioned formation, employing will have the intermediate layer film forming of mono-crystalline structures by plasma with the method that raw material activates on substrate, in addition, by being defined in optimum range as the dividing potential drop of the nitrogen of V group element, the ground film forming that can have good uniformity goes out the intermediate layer, and described intermediate layer can adopt the MOCVD film forming to go out the III group-III nitride semiconductor of well-crystallized thereon.
Therefore, can on substrate, grow intermediate layer that forms by the good III group-III nitride compound of crystallinity and the semiconductor layer that forms by the III group-III nitride semiconductor expeditiously, the productivity ratio excellence, the III group-III nitride semiconductor light-emitting component that can obtain cheapness and have the excellent characteristics of luminescence.
Description of drawings
Fig. 1 is the figure that pattern ground illustrates III group-III nitride semiconductor light-emitting component one example that the present invention relates to, and is the skeleton diagram of the cross section structure of expression laminated semiconductor.
Fig. 2 is the figure of III group-III nitride semiconductor light-emitting component one example that the present invention relates to of the explanation of pattern, is the figure of expression planar structure.
Fig. 3 is the figure of III group-III nitride semiconductor light-emitting component one example that the present invention relates to of the explanation of pattern, is the figure of expression cross section structure.
Fig. 4 is the skeleton diagram that the lamp of the III group-III nitride semiconductor light-emitting component formation that the present invention relates to is used in the explanation of pattern.
Fig. 5 is the figure of an example of the III group-III nitride semiconductor method of manufacturing luminescent device that the present invention relates to of the explanation of pattern, is the skeleton diagram of expression sputter equipment structure.
Fig. 6 is the figure of the embodiment of the III group-III nitride semiconductor light-emitting component that the present invention relates to of explanation, is (0002) face of expression basalis and (10-10) the wide curve chart of XRC spectrum half value of face.
The drawing reference numeral explanation
1-III group-III nitride semiconductor light-emitting component, 10-laminated semiconductor, 11-substrate, 11a-surface, 12-intermediate layer, 13-basalis, 14-n type semiconductor layer, 14a-basalis, 15-luminescent layer, 16-p type semiconductor layer, 17-light transmission positive pole, 3-lamp
Embodiment
Below, Yi Bian suitably with reference to Fig. 1～6, Yi Bian the manufacture method of the III group-III nitride semiconductor light-emitting component that the present invention relates to and an execution mode of III group-III nitride semiconductor light-emitting component and lamp are described.
The III group-III nitride semiconductor light-emitting component of present embodiment (below, sometimes be called for short light-emitting component) manufacture method, be to make its reaction by the gas and the metal material activation that will contain V group element by plasma, thereby film forming goes out the intermediate layer 12 that is formed by III group-III nitride compound on substrate 11, on this intermediate layer 12, stack gradually the n type semiconductor layer 14 that forms by the III group-III nitride semiconductor, the method of luminescent layer 15 and p type semiconductor layer 16, be that to make above-mentioned V group element be nitrogen, making the gas branch rate of the nitrogen in the above-mentioned gas when forming intermediate layer 12 is greater than 20% and in the scope below 99%, and the method that intermediate layer 12 is formed as single crystal organization.
[laminated construction of light-emitting component]
The III group-III nitride semiconductor light-emitting component of present embodiment, be to react by plasma-activated by the gas and the metal material that will contain V group element, thereby film forming goes out the intermediate layer 12 that is formed by III group-III nitride compound on substrate 11, on this intermediate layer 12, stack gradually the n type semiconductor layer 14 that forms by the III group-III nitride semiconductor, the light-emitting component that luminescent layer 15 and p type semiconductor layer 16 form, intermediate layer 12 is that to make above-mentioned V group element be nitrogen, the gas branch rate that makes the nitrogen in the above-mentioned gas is for greater than 20% and the layer that goes out in the scope film forming below 99%, and be single crystal organization, thereby roughly constitute.
Fig. 1 is the figure that is used to illustrate III group-III nitride semiconductor light-emitting component one example that the present invention relates to, and is the summary sectional view that is illustrated in an example of the laminated semiconductor that has formed the III group-III nitride semiconductor on the substrate.
Laminated semiconductor 10 shown in Fig. 1 example is following formation, promptly on formed intermediate layer 12 on the substrate 11, be laminated with the basalis 14a that forms by the III group-III nitride semiconductor, on substrate 11, stack gradually intermediate layer 12, comprise basalis 14a, the n type semiconductor layer 14 of n type contact layer 14b and n type cover layer 14c, the luminescent layer 15 that barrier layer 15a and trap layer 15b alternately are laminated, the p type semiconductor layer 16 that comprises p type cover layer 16a and p type contact layer 16b form.
In addition, 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, form positive terminal pad 18 more thereon, simultaneously formedly on the n type contact layer 14b of n type semiconductive layer 14 expose stacked negative pole 19 on the regional 14d and can constitute light-emitting component 1.
Below, the laminated construction of the III group-III nitride semiconductor light-emitting component of present embodiment is described in detail.
[substrate]
In the present embodiment, as the substrate 11 of epitaxial growth III group-III nitride semiconductor crystallization from the teeth outwards, there is no particular limitation, can select various materials to use, 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.
Moreover, do not use ammonia and film forming is carried out in the intermediate layer, adopt the method for using ammonia with basalis film forming described later simultaneously, in addition, in the aforesaid substrate material, use is by at high temperature contacting the occasion of the known oxide substrate that causes the chemical modification, metal substrate etc. with ammonia, the intermediate layer of present embodiment plays a role as coating, therefore considers it is effective from the viewpoint of the chemical modification that prevents substrate.
[intermediate layer]
The laminated semiconductor 10 of present embodiment, by raw metal and the gas that contains V group element are reacted by plasma-activated, thereby film forming goes out the intermediate layer 12 that is formed and had mono-crystalline structures by III group-III nitride compound on substrate 11.Adopt as the use plasma of present embodiment the film of method film forming of raw metal, have the effect that easy acquisition is orientated.
The III group-III nitride semiconductor element of LED, LD etc. must be at certain certain direction streaming current of determining.For this reason, require III group-III nitride semiconductor element that good crystallinity and orientation are arranged.Because the epitaxial growth on intermediate layer 12 of III group-III nitride semiconductor element, so intermediate layer 12 needs good crystallinity and orientation similarly.
Adopt mocvd method to make the occasion of III group-III nitride semiconductor growth,, therefore, need become the substrate of template in order to make the film orientation because mocvd method is that the metal organic molecule is decomposed and the method for laminated metal element.For this reason, 12 is the occasion of the low temperature buffer layer of growth on substrate 11 in the intermediate layer, and substrate becomes substrate, and therefore the substrate that can use is limited.
On the other hand, adopt reactive sputtering to make the occasion of III group-III nitride semiconductor growth, the charged particle that is bombarded in the plasma not necessarily exists with state of atom, also as the charged particle existence with key of dimer etc.Such charged particle becomes the raw material when forming film.Therefore in addition, such charged particle has moment, is subjected to the electric field effects that caused by sputter, has specific anisotropy and is deposited on the substrate 11.Because this anisotropy, film presents orientation texture, therefore can both adopt sputtering method to form alignment films in the occasion of using any substrate.
More than at least 60% of surperficial 11a of intermediate layer 12 necessary covered substrates 11 preferably covers more than 80%.Consider from function aspects, preferably form in the mode that covers more than 90% as the coating of substrate 11.In addition, most preferably 100% of covering surfaces 11a, promptly seamlessly the surperficial 11a ground of covered substrate 11 forms intermediate layer 12.
When the zone of the surperficial 11a of intermediate layer 12 covered substrates 11 diminishes, substrate 11 exposes widely, therefore do not play a role as coating, between raw semiconductor that makes III group-III nitride semiconductor crystalline growth and substrate, react, might damage the flatness of formed n type semiconductor layer on intermediate layer 12.
Moreover when forming the intermediate layer on substrate 11, the surperficial 11a ground that can only cover substrate 11 forms, surperficial 11a and formation laterally that also can covered substrate 11.In addition, consider that most preferably the surperficial 11a of covered substrate 11, side and ground, the back side form from function aspects as coating.
When adopting mocvd method; sometimes unstripped gas is around the side or the back side to substrate; therefore adopt the mocvd method film forming to go out arbitrary layer the occasion of each layer that forms by the crystallization of III group-III nitride semiconductor described later; for fear of the reaction of unstripped gas and substrate, preferably also can protective substrate side or formation intermediate layer, ground, the back side.
In addition, consider that from the aspect of buffering function preferred interlayer 12 is mono-crystalline structures.As above-mentioned, the crystallization of III group-III nitride compound has the crystallization of hexagonal crystal system, and forming with hexagon prism is basic tissue.The crystallization of III group-III nitride compound by the condition of control film forming etc., can film forming go out along the crystallization of direction growth in the face.Film forming goes out to have the occasion in the intermediate layer 12 of such mono-crystalline structures on substrate 11, because the pooling feature in intermediate layer 12 plays a role effectively, therefore the III nitride semiconductor layer of film forming becomes and has good orientation and crystalline crystalline film thereon.
The thickness in intermediate layer 12 is preferably the scope of 20～80nm.Thickness by making intermediate layer 12 is this scope, can make to have good crystalline intermediate layer 12 and become and have specific anisotropic alignment films, can carry out film forming at short notice on substrate 11.
The thickness in intermediate layer 12 might be able to not obtain having good crystalline film as having specific anisotropic alignment films during less than 20nm, simultaneously as the function of above-mentioned coating insufficient.
In addition, to form the occasion in intermediate layer 12 above the thickness of 80nm, also might be able to not obtain having good crystalline film as having specific anisotropic alignment films, though the while is as the not variation of function of coating, but the film forming processing time is elongated, might productivity ratio reduce.
Intermediate layer 12 is preferably the composition that contains Al, is preferably especially by constituting that AlN forms.
As the material that constitutes intermediate layer 12, so long as the III group-III nitride semiconductor of representing by general formula AlGaInN, no matter be which kind of material can use, in addition, also can be for contain the formation of As, P as V family.
Making intermediate layer 12 is the occasion that contains the composition of Al, wherein, is preferably GaAlN, and at this moment, preferred Al component is more than 50%.
In addition, by making intermediate layer 12, can become the layer of orientation well for by forming that AlN constitutes.
[laminated semiconductor]
As shown in Figure 1, the laminated semiconductor 10 of present embodiment, Jie has aforesaid intermediate layer 12 and is laminated with the semiconductor layer 20 that comprises the n type semiconductor layer 14, luminescent layer 15 and the p type semiconductor layer 16 that are formed by nitride-based compound semiconductor on substrate 11.
In addition, n type semiconductor layer 14 has the basalis 14a that is formed by the III group-III nitride semiconductor at least, and basalis 14a is laminated on the intermediate layer 12.
On the basalis 14a that forms by the III group-III nitride semiconductor, can constitute as described above as shown in Figure 1 laminated semiconductor 10 such have functional crystallization laminated construction.For example, in the occasion of the semiconductor laminated structure that is formed for light-emitting component, can the stacked Si of being doped with, Ge, the n type conductive layer of the n type alloy of Sn etc., be doped with magnesium etc. p type alloy p type conductive layer etc. and form laminated semiconductor.In addition, as material, luminescent layer etc. can use InGaN, and cover layer etc. can use AlGaN.
By further forming III group-III nitride semiconductor crystallizing layer at basalis 14a in this wise, can make the wafer with semiconductor laminated structure of the making 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 many 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) expression gallium nitride compound semiconductor, also comprise the gallium nitride compound semiconductor that these are known among the present invention, can be without any restrictedly using 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 can also contain other III family element except Al, Ga and In, also can contain elements such as Ge, Si, Mg, Ca, Zn, Be, P and As required.In addition, the element that is not limited to add wittingly also contains sometimes depend on membrance casting condition etc. and impurity that contains inevitably and the trace impurity that contains in raw material, reaction tube material.
" n type semiconductor layer "
N type semiconductor layer 14 is laminated on the above-mentioned intermediate layer 12 usually, is made of basalis 14a, n type contact layer 14b and n type cover layer 14c.Moreover, but n type contact layer double as basalis and/or n type cover layer, but but basalis also double as n type contact layer and/or n type cover layer.
(basalis)
Basalis 14a is formed by the III group-III nitride semiconductor, stacked ground film forming on intermediate layer 12.
As the material of basalis 14a, can use with by the different material in the intermediate layer 12 of film forming on substrate 11, but preferably by Al XGa 1-XN layer (0≤X≤1, preferred 0≤X≤0.5, more preferably 0≤X≤0.1) constitutes.
As the material that is used for basalis 14a, can use the III group-III nitride compound that contains Ga, i.e. GaN based compound semiconductor, AlGaN that can preferably use or GaN especially.
In addition, basalis 14a need make the dislocation cyclisation inherit the crystallinity in intermediate layer 12 to avoid former state ground by migration, also can enumerate the GaN based compound semiconductor of the above-mentioned Ga of containing, preferred especially AlGaN or GaN as such material.
The thickness of basalis 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.For this thickness obtains the good Al of crystallinity when above easily XGa 1-XThe N layer.
For basalis 14a, can be the formation that is doped with alloy as required, also can be the formation of the alloy that undopes.
Use the occasion of conductive boards at substrate 11, as mentioned above, 14a mixes to basalis, and the layer structure that makes basalis 14a be streaming current longitudinally, can form the structure that electrode is set on the chip two sides of light-emitting component thus.
In addition, use the occasion of insulating properties substrate at substrate 11, owing to become employing forms electrode on the identical faces of the chip of light-emitting component chip structure, therefore being situated between on substrate 11 has intermediate layer 12 and stacked basalis 14a can be plain crystallization, and crystallinity becomes good at this moment.
(n type contact layer)
As n type contact layer 14b, preferably with basalis 14a similarly by Al XGa 1-XN layer (0≤X≤1, preferred 0≤X≤0.5, more preferably 0≤X≤0.1) constitutes.In addition, preferably be doped with n type impurity, with 1 * 10 17～1 * 10 19/ cm 3, preferably with 1 * 10 18～1 * 10 19/ cm 3Concentration when containing n type impurity, be preferred keeping with the good Ohmic contact of negative pole, suppressing that crackle takes place, keeps aspect the good crystallinity.Be not particularly limited as n type impurity, for example can enumerate Si, Ge and Sn etc., preferably Si and Ge.Growth temperature is identical with basalis.In addition, as mentioned above, n type contact layer 14b also can be the formation of double as basalis.
Constitute the gallium nitride compound semiconductor of basalis 14a and n type contact layer 14b, preferably same composition is set in 0.1～20 μ m with their thickness of total, preferably sets at 0.5～15 μ m, more preferably is set in the scope of 1～12 μ m.When thickness is this scope, can keep semi-conductive crystallinity well.
(n type cover layer)
N type cover layer 14c preferably is set between n type contact layer 14b and luminescent layer described later 15.By n type cover layer 14c is set, can improve the deterioration of the flatness of surperficial generation of n type contact layer 14b.N type cover layer 14c can be formed by AlGaN, GaN, GaInN etc.In addition, also can be the heterogeneous joint of their structure, stacked superlattice structure repeatedly.In the occasion that is GaInN, hope is bigger than the band gap of the GaInN of luminescent layer 15 certainly.
There is no particular limitation for the thickness of n type cover layer 14c, and the scope of 5～500nm preferably is more preferably the scope of 5～100nm.
In addition, the n type concentration of dopant of n type cover layer 14c is preferably 1 * 10 17～1 * 10 20/ cm 3Scope, be more preferably 1 * 10 18～1 * 10 19/ cm 3Scope.
When concentration of dopant is this scope, preferred aspect the operating voltage of keeping good crystallinity and reduction light-emitting component.
" p type semiconductor layer "
P type semiconductor layer 16 is made of p type cover layer 16a and p type contact layer 16b usually.Yet p type contact layer also can double as p type cover layer.
(p type cover layer)
As p type cover layer 16a, be the composition bigger than the band-gap energy of luminescent layer 15, then there is no particular limitation so long as charge carrier can be enclosed the composition of luminescent layer 15, preferably enumerates Al dGa 1-dThe composition of N (0≤d≤0.4, preferred 0.1≤d≤0.3).When p type cover layer 16a is formed by such AlGaN, preferred aspect charge carrier inclosure luminescent layer 15.There is no particular limitation for the thickness of p type cover layer 16a, and preferably 1～400nm is more preferably 5～100nm.The p type concentration of dopant of p type cover layer 16a preferably 1 * 10 18～1 * 10 21/ cm 3, be more preferably 1 * 10 19～1 * 10 20/ cm 3When p type concentration of dopant is above-mentioned scope, crystallinity is reduced also can obtain good p type crystallization.
(p type contact layer)
As p type contact layer 16b, be to contain Al at least eGa 1-eThe gallium nitride system compound semiconductor layer of N (0≤e＜0.5, preferred 0≤e≤0.2, more preferably 0≤e≤0.1).When Al consists of above-mentioned scope, in that to keep the good ohmic of good crystallinity with p Ohmic electrode (with reference to optically transparent electrode 17 described later) preferred aspect contacting.
In addition, with 1 * 10 18～1 * 10 21/ cm 3When the concentration of scope contains p type alloy, keeping good Ohmic contact, preventing that crackle from taking place, keeping aspect the good crystallinity preferred, is more preferably 5 * 10 19～5 * 10 20/ cm 3Scope.
There is no particular limitation as p type impurity, for example preferably enumerates Mg.
There is no particular limitation for the thickness of p type contact layer 16b, and preferably 10～500nm is more preferably 50～200nm.When thickness is this scope, preferred aspect luminous power output.
" luminescent layer "
Luminescent layer 15 is to be layered on the n type semiconductor layer 14, and the layer of stacked thereon p type semiconductor layer 16, as shown in Figure 1, the barrier layer 15a that forms by gallium nitride compound semiconductor and alternately repeat stacked by the trap layer 15b that the gallium nitride compound semiconductor that contains indium forms, and the sequential cascade ground that is configured in n type semiconductor layer 14 sides and p type semiconductor layer 16 sides by barrier layer 15a forms.
In addition, in the example that Fig. 1 represents, luminescent layer 15 is following formation, and promptly the trap layer 15b of 6 layers barrier layer 15a and 5 layers alternately repeats stackedly, and barrier layer 15a is configured in the superiors and the orlop of luminescent layer 15, and trap layer 15b is configured between each barrier layer 15b.
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, there is no particular limitation as the thickness of luminescent layer 15 integral body, but preferably can obtain the thickness of the degree of quantum effect, i.e. the critical film thickness scope.For example, the thickness of luminescent layer 15 is the scope of 1～500nm preferably, is more preferably the thickness about 100nm.When thickness is this scope, help the raising of luminous power output.
" 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.
There is no particular limitation as the material of light transmission positive pole 17, can adopt the habitual means of knowing in the art that ITO (In is set 2O 3-SnO 2), AZO (ZnO-Al 2O 3), IZO (In 2O 3-ZnO), GZO (ZnO-Ga 2O 3) wait material.In addition, its structure also comprise existing known structure interior can be without any the material that restrictedly uses any structure.
Light transmission positive pole 17 can with on the p type semiconductor layer 16 that covers doped with Mg roughly all the mode of faces form, also can separate the gap and form clathrate, tree shape.After forming light transmission positive pole 17, implement sometimes with alloying, the transparent thermal annealing that turns to purpose.But also can not implement this thermal annealing.
" positive terminal pad and negative pole "
Positive terminal pad 18 is formed in the electrode on the above-mentioned light transmission positive pole 17.
As the material of positive terminal pad 18, the well-known various structures that are to use Au, Al, Ni and Cu etc. can be without any the electrode that restrictedly uses these well-known materials, structure.
The thickness of positive terminal pad 18 is preferably in the scope of 100～1000nm.In addition, on the characteristic of pad, zygosity uprised when thickness was big, and therefore more preferably the thickness of positive terminal pad 18 is more than the 300nm, considers more preferably below the 500nm from the viewpoint of manufacturing cost.
Negative pole 19 in n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16 are stacked gradually semiconductor layer on substrate 11, is formed in contact with the n type contact layer 14b of n type semiconductor layer 14.
For this reason, when forming negative pole 19, remove the part of p type semiconductor layer 16, luminescent layer 15 and n type semiconductor layer 14 and form the regional 14b that exposes of n type contact layer 14b, on this zone, form negative pole 19.
As the material of negative pole 19, the negative pole of well-known various compositions and structure can be without any restrictedly using these well-known negative poles, can adopt the habitual means setting of knowing in the art.
[manufacture method of III group-III nitride semiconductor light-emitting component]
The manufacture method of the III group-III nitride semiconductor light-emitting component of present embodiment, as mentioned above, be it to be reacted by the gas and the metal material activation that will contain V group element by plasma, thereby film forming goes out the intermediate layer 12 that is formed by III group-III nitride compound on substrate 11, on this intermediate layer 12, stack gradually n type semiconductor layer 14, the method of luminescent layer 15 and p type semiconductor layer 16, be that to make above-mentioned V group element be nitrogen, making the gas branch rate of the nitrogen in the above-mentioned gas when forming intermediate layer 12 is greater than 20% and in the scope below 99%, and the method that above-mentioned intermediate layer 12 is formed as single crystal organization.
The manufacture method of present embodiment, be when on substrate 11, making III group-III nitride semiconductor crystallization epitaxial growth, for example adopt sputtering method, will be by raw material film forming on substrate 11 plasma-activated and that carried out reaction, thereby form the method in intermediate layer 12, by the gas branch rate that makes the nitrogen in the gas is above-mentioned scope and with intermediate layer 12 film forming, make to have good crystalline intermediate layer 12 and become and have specific anisotropic alignment films, can on substrate 11, carry out film forming at short notice.Thus, can be on intermediate layer 12 the good III group-III nitride semiconductor of grown junction crystallinity expeditiously.
In addition, in the example shown in the present embodiment, adopted following method: after adopting sputtering method to form intermediate layer 12, adopt mocvd method on intermediate layer 12, to form the basalis 14a of n type semiconductor layer 14, adopt sputtering method to form each layer of n type contact layer 14b and n type cover layer 14c, the employing mocvd method forms the luminescent layer 15 above it, then, adopts sputtering method to form and constitutes the p type cover layer 16a of p type half storey body layer 16 and each layer of p type contact layer 16b.
" formation in intermediate layer "
When on substrate 11, forming intermediate layer 12, preferably substrate is carried out the preliminary treatment of wet type.For example, to the substrate 11 that is formed by silicon, the RCA washing methods that employing is known etc. make the surface become the hydrogen end, and film-forming process is stable thus.
In addition, import to substrate 11 in the reactor (sputter equipment) after, before forming intermediate layer 12, can adopt the method for reverse sputtering etc. to carry out preliminary treatment.Particularly, can be by substrate 11 be exposed to Ar, N 2Plasma in adjust the surface.
For example, by making Ar gas, N 2The action of plasma of gas etc. can be removed attached to substrate 11 lip-deep organic substances, oxide in substrate 11 surfaces.Under this occasion,, then act on to plasma particle efficient rate substrate 11 if between substrate 11 and chamber, apply voltage.
By substrate 11 is implemented such preliminary treatment, can on the surperficial 11a of substrate 11 is comprehensive, form intermediate layer 12, can improve the crystallinity of the film of film forming thereon.
In addition, to the preliminary treatment of substrate 11, preferably by carrying out in the aforesaid plasma treatment of carrying out in the atmosphere of ion component and uncharged free radical composition that is mixed with.
At this, when the dirt of organic substance, oxide etc. is removed on the surface of substrate, for example, supply with the occasion of ion component etc. individually to substrate surface, exist energy strong excessively, substrate surface is caused damage, make the problem of the quality reduction of the crystallization of growing on the substrate.
In the present invention, making the preliminary treatment to substrate 11 is to adopt in the aforesaid plasma treatment method of carrying out in the atmosphere of ion component and free radical composition that is mixed with, act on substrate 11 by the reactive material that makes energy with appropriateness, can be not cause damage and carry out removing of dirt etc. substrate 11 surfaces, as the mechanism that can obtain this effect, can think by using the few plasma of ratio of ion component, can suppress damage that substrate surface is caused, by making action of plasma in substrate surface, can remove crude removal effectively, or the like.
As the method for on substrate 11, intermediate layer 12 being carried out film forming, except applying under the specific vacuum degree the sputtering method that high voltage discharges, for example, thereby pulsed laser deposition (PLD) method of plasma takes place, pulsed electron beam deposition (PED) method of plasma etc. takes place by irradiating electron beam in the laser that can enumerate mocvd method, irradiation high-energy-density, can suitably select to use, and sputtering method is the easiest and be suitable for a large amount of productions, is preferable methods therefore.
Moreover when known employing sputtering method used the nitrogen as V group element to carry out film forming, nitrogen was adsorbed on target (metal material) surface (with reference to Mat.Res.Soc.Symp.Proc, Vol.68,357,1986).Usually, the occasion that the target of use metal material carries out sputter is if use the DC sputtering method, then preferred aspect film forming efficiency, but owing to nitrogen attached to the charging that causes the target surface on the target, might the film forming speed instability, therefore preferably adopt pulsed D C sputtering method or adopt the RF sputtering method.
In sputtering method, generally can use the technology that efficient is improved by plasma is enclosed, as the method that is used for target is used with departing from, while the preferred magnet positions that makes negative electrode that adopts moves the RF sputtering method that carries out film forming in target.The movement technique of concrete magnet can suitably be selected according to sputter equipment, for example, magnet is shaken, or it is rotatablely moved.
The RF sputter equipment 40 of example shown in Figure 5, magnet 42 are configured in the below (below of Fig. 5) of metallic target 47, and these magnet 42 utilizations are saved illustrated drive unit and shaken below metallic target 47.Supply with nitrogen and argon gas in chamber 41, film forming goes out the intermediate layer on the substrate 11 that is installed on the heater 44.At this moment, as mentioned above, because magnet 42 shakes below metallic target 47, therefore the plasmas of enclosing in the chamber 41 move, except the surperficial 11a of substrate 11, also can to the side equably film forming go out the intermediate layer.
Moreover, adopting sputtering method intermediate layer 12 to be carried out the occasion of film forming, from keeping crystallinity well by the control reaction, can stably reproducing its good crystallinity aspect consideration, more preferably adopt the reactive sputtering that nitrogenous gas is circulated in reactor to carry out the method for film forming.
In addition, adopt sputtering method, especially adopt reactive sputtering that the occasion of film forming is carried out in intermediate layer 12,, can enumerate pressure in nitrogen partial pressure, the stove etc. as the important parameter beyond the temperature of substrate 11.
The gas of the nitrogen in the nitrogenous gas divides rate, that is, the nitrogen flow is with respect to nitrogen (N 2) with the ratio of the flow of Ar, preferred nitrogen surpasses 20%.Nitrogen is 20% when following, and the amount of nitrogen is few and metal is separated out on substrate 11, can not become the desired crystalline texture of III group-III nitride compound as intermediate layer 12.In addition, when being nitrogen greater than 99% flow-rate ratio, the amount of Ar is very few, and sputtering rate reduces significantly and be not preferred.In addition, the gas of the nitrogen in the nitrogenous gas divides rate more preferably greater than 40% and in the scope below 99%, most preferably is greater than 75% and in the scope below 99%.
In the present embodiment,, can suppress the migration on the substrate 11, thus, can suppress self-organization, make intermediate layer 12 suitably become single crystal organization by on substrate 11, supplying with the active nitrogen reactive material with high concentration.In intermediate layer 12,, can be controlled at the crystallinity of the stacked semiconductor layer that forms by GaN on it well by the tissue that suitable control is made of monocrystalline.
Pressure in the stove when in addition, adopting sputtering method that film forming is carried out in intermediate layer 12 is preferably more than the 0.2Pa.Pressure in this stove is during less than 0.2Pa, and the kinetic energy that the reactive material of generation has becomes excessive, formed intermediate layer membranous insufficient.In addition, there is no particular limitation for upper limit of pressure in this stove, but when being 0.8Pa when above, help the dimer charged particle of film orientation to be subjected to the interaction of the charged particle in the plasma, the pressure in the therefore preferred stove is preferably the scope of 0.2～0.8Pa.
In addition, the film forming speed when film forming is carried out in intermediate layer 12 is preferably the scope of second 0.01nm/ second～10nm/.During second, film can not become layer to film forming speed, and grows into island less than 0.01nm/, surface that might can not covered substrate 11.Film forming speed surpasses 10nm/ during second, and film does not become crystalline solid and becomes amorphous.
The temperature of the substrate 11 when film forming is carried out in intermediate layer 12 is preferably the scope of room temperature～1000 ℃, more preferably 200～800 ℃ scope.Down in limited time intermediate layer 12 is can not covered substrate 11 comprehensive less than above-mentioned for the temperature of substrate 11, and substrate 11 surfaces might be exposed.The temperature of substrate 11 surpasses above-mentioned going up in limited time, and the migration of metal material is too active, considers from the functional point of view as resilient coating, might become unaccommodated layer.
Moreover the room temperature that illustrates among so-called the present invention is to the environment of technology etc. the also temperature of influence, as concrete temperature, is 0～30 ℃ scope.
Employing is with the one-tenth embrane method of metal material plasma, when going out mixed crystal as the intermediate layer film forming, for example, the mixture (can form alloy) that adopts the metal material contain Al etc. the method as target is arranged, the method that 2 targets that also can adopt preparation to be made of different materials side by side carry out sputter.For example,, use the target of composite material,, a plurality of targets are arranged on indoor getting final product forming the occasion of forming different several films in the occasion of the film that forms definite composition.
As the gas of nitrogenous (V group element) that use in the present embodiment, can be without any restrictedly using general known nitrogen compound, ammonia, nitrogen (N 2) since simple to operate, simultaneously less expensive, obtain easily, therefore 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, detector, and, must make the material of the member that uses in the reaction unit be the high material of chemical stability.
In addition, use nitrogen (N 2) as the occasion of raw material, as device can be easy to use device, but can not obtain high reaction speed.Yet, if adopt by electric field, heat etc., can access film forming speed lower than ammonia but degree that on industrial production, can utilize with the method that nitrogen decomposes the back gatherer, if therefore consider and the taking into account of installation cost, then be most preferred nitrogenous source.
In addition, as mentioned above, preferably the mode with the side of covered substrate 11 forms intermediate layer 12.In addition, most preferably form intermediate layer 12 with the side of covered substrate 11 and the mode at the back side.Yet, adopt existing film build method that the occasion of film forming is carried out in the intermediate layer, need carry out the most nearly about 6 times～8 times film forming and handle, become long operation.As the film build method beyond this film build method, also can consider by not keeping substrate to be arranged on indoorly, carry out the method for film forming on comprehensively at substrate, but in the occasion that need heat substrate, it is complicated that device might become.
Therefore, for example can consider by substrate being shaken or it is rotatablely moved, while the method for carrying out film forming is changed with respect to the sputter direction of filmogen in the position that makes substrate.By adopting such method, can carry out film forming to the surface and the side of substrate with operation once, then, and by carrying out film formation process to substrate back, can be comprehensive to add up to 2 times operation covered substrate.
In addition, also can adopt: the filmogen source is constituting of being taken place by large-area generation source, and moves by the occurrence positions that makes material, substrate is moved and carries out the method for film forming at substrate on comprehensively.As such method, can enumerate as mentioned above by magnet being shaken or it being rotatablely moved, while the position of the magnet that makes negative electrode at the indoor mobile RF sputtering method that carries out film forming, in addition, adopt such RF sputtering method to carry out the occasion of film forming, also can adopt the method that substrate-side and this two side of cathode side are moved.In addition, if the cathode arrangement by will the source taking place as material near substrate, is not supplied with the plasma that takes place with pencil to substrate but is become the formation of supplying with in the mode that encases substrate, substrate surface and side film forming simultaneously then.
" formation of semiconductor layer "
In the manufacture method of present embodiment, on the intermediate layer 12 of film forming on the substrate 11, form the semiconductor layer 20 that forms by the III group-III nitride semiconductor.In this example, among semiconductor layer 20, after adopting mocvd method to form the basalis 14a of n type semiconductor layer 14, adopt sputtering method to form each layer of n type contact layer 14b and n type cover layer 14c, the employing mocvd method forms the luminescent layer 15 on it, then, adopt reactive sputtering to form the p type cover layer 16a of formation p type semiconductor layer 16 and each layer of p type contact layer 16b.
In the present embodiment, there is no particular limitation for the growing method of the gallium nitride compound semiconductor when forming semiconductor layer 20, except the reactive sputtering of the manufacture method of above-mentioned present embodiment and the manufacturing installation that adopts above-mentioned present embodiment, can also adopt MOCVD (metal organic chemistry vapour phase deposition process), HVPE (hydride vapor growth method), the MBE known all methods that make nitride semiconductor growing such as (molecular beam epitaxial growth methods).As preferred growing method, consider it is mocvd method from the viewpoint of film thickness monitoring, the property produced in enormous quantities.When adopting 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), can use ammonia (NH as the N source of V family raw material as the In source 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) 4Organic germanium compounds such as Ge).When adopting the MBE method, the germanium of element state also can be as the doped source utilization.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).
Aforesaid gallium nitride compound semiconductor can be except Al, Ga and In, also contains the formation of other III family element.The doped chemical that can contain Ge, Si, Mg, Ca, Zn, Be etc. as required.In addition, the element that is not limited to add wittingly also contains sometimes depend on membrance casting condition etc. and impurity that contains inevitably and the trace impurity that contains in raw material, reaction tube material.
(formation of n type semiconductor layer)
When forming the semiconductor layer 20 of present embodiment, at first, adopt existing known mocvd method on intermediate layer 12, to form the basalis 14a of n type semiconductor layer 14 stackedly.Then, adopt sputtering method on basalis 14a, to form n type contact layer 14b and n type cover layer 14c.At this moment, each layer of n type contact layer 14b and n type cover layer 14c can use same sputter equipment to carry out film forming.
The method of the basalis 14a that forms as the III group-III nitride semiconductor that on substrate 11, forms by monocrystalline, has following method, promptly, as present embodiment, adopt sputtering method film forming on substrate 11 to go out the intermediate layer 12 that forms by AlN, adopt mocvd method on this intermediate layer, to form the GaN layer of monocrystalline under than the high high temperature of the temperature that forms intermediate layer 12.
In the present embodiment, adopt above-mentioned method after film forming goes out intermediate layer 12 on the substrate 11, before forming basalis 14a, do not need to carry out annealing in process especially.Yet, usually carry out the occasion of the film forming of III group-III nitride semiconductor at the gas chemistry film build method that adopts MOCVD, MBE, VPE etc., be accompanied by film forming, through the stabilization procedures of temperature-rise period and temperature and processed, but in these processes, make the unstripped gas of V family more, therefore as a result of, produce the annealing effect sometimes in the situation of indoor circulation.
In addition, as the carrier gas of this moment circulation, can be without any restrictedly using general carrier gas, also can use the hydrogen, the nitrogen that in the gas chemistry film build method of MOCVD etc., use widely.Yet, as the occasion of the chemically more active hydrogen of carrier gas use, might damage the flatness of crystallinity, crystal surface, the therefore preferred shortening processing time.
There is no particular limitation as the method for stacked basalis 14a, as each above-mentioned method, so long as can produce the crystalline growth method of the cyclisation of dislocation, just can be without any restrictedly adopting.Especially mocvd method, MBE method, VPE method owing to can produce aforesaid migration, therefore can form the film of well-crystallized, thereby preferred.Wherein, mocvd method can access the best film of crystallinity aspect can more preferably use.
In addition, also can adopt sputtering film-forming to go out the basalis 14a that forms by the III group-III nitride semiconductor.In the occasion that adopts sputtering method, compare with mocvd method, MBE method, can make device is easy formation.
Moreover, adopting sputtering method to form the occasion of basalis 14a, keeping crystallinity well by the control reaction, can stably reproduce its good crystallinity aspect, more preferably adopt the reactive sputtering that V family raw material (nitrogen) is circulated in reactor to carry out the method for film forming.
The temperature of the substrate 11 when forming basalis 14a, that is, the growth temperature of basalis 14a is preferably more than 800 ℃.This is because pass through to improve the temperature of the substrate 11 when forming basalis 14a, and the migration of atom takes place easily, carries out the cause of the cyclisation of dislocation easily.More preferably more than 900 ℃, most preferably be more than 1000 ℃.
In addition, the temperature of the substrate 11 when forming basalis 14a need be the low temperature of temperature of decomposing than crystallization, therefore is preferably less than 1200 ℃.
Therefore, the growth temperature of above-mentioned basalis 14a can be preferably more than 800 ℃ and less than 1200 ℃, more preferably more than 900 ℃ and less than 1200 ℃, most preferably is more than 1000 ℃ and less than 1200 ℃ temperature range.So long as the temperature of the substrate 11 when forming basalis 14a is in these temperature ranges, just can access the good basalis 14a of crystallinity.
Moreover, about basalis 14a,, and carry out film forming with non-doping way not to the doped chemical that forms by donor impurity of indoor supply Si of sputter equipment etc.On the other hand, about n type contact layer 14b and n type cover layer 14c,, can access and add the GaN layer that donor impurity, conductivity are controlled so as to the n type by carrying out film forming by the doped chemical that donor impurity forms to indoor supply.
(formation of luminescent layer)
Adopt existing known mocvd method on n type cover layer 14c, to form luminescent layer 15.As shown in Figure 1, the luminescent layer 15 that forms in the present embodiment has and starts from GaN barrier layer, the laminated construction of GaN barrier layer finally, 6 layers the barrier layer 15a that forms by the GaN by doping Si and by the In of non-doping 0.2Ga 0.85 layers of trap layer 15b that N forms are alternately stacked and form.
(formation of p type semiconductor layer)
Adopt manufacture method, on luminescent layer 15, that is, on the barrier layer 15a of the superiors that become luminescent layer 15, form the p type semiconductor layer 16 that comprises p type cover layer 16a and p type contact layer 16b by reactive sputtering as above-mentioned present embodiment.
In the present embodiment, at first, go up the Al that forms by the Mg that mixed at luminescent layer 15 (the barrier layer 15a of the superiors) 0.1Ga 0.9The p type cover layer 16a that N forms forms the Al by the Mg that mixed on this p type cover layer 16a 0.02Ga 0.98The p type contact layer 16b that N forms.At this moment, p type cover layer 16a and the stacked of p type contact layer 16b can be used same device.
In the film forming of the p type semiconductor layer 16 that comprises these p types cover layer 16a and p type contact layer 16b is handled, adopt the manufacture method of above-mentioned present embodiment, carry out film forming by in sputtering chamber 41, supplying with the doped chemical that forms by acceptor impurity (Mg), can obtain adding acceptor impurity, conductivity is controlled so as to p type and GaN layer (p type semiconductor layer 16).
" formation of light transmission positive pole "
Adopt aforesaid method, on p type contact layer 16, form the light transmission positive pole 17 that constitutes by ITO at the laminated semiconductor 10 that is laminated with intermediate layer 12 and semiconductor layer on the substrate 11.
As the formation method of light transmission positive pole 17, there is no particular limitation, can adopt the habitual means of knowing in the art to be provided with.In addition, its structure comprises that also existing known structure can be without any the light transmission positive pole that restrictedly uses any structure.
In addition, as mentioned above, the material of light transmission positive pole 17 is not limited to ITO, can use the material of AZO, IZO, GZO etc. 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 terminal pad and negative pole "
On the light transmission positive pole 17 that is formed on the laminated semiconductor 10, also form positive terminal pad 18.
This positive terminal pad 18, for example can by adopt existing known method from the face side of light transmission positive pole 17 stack gradually Ti, Al, each material of Au forms.
In addition, when forming negative pole 19, at first, remove the part of the luminescent layer 15, p type semiconductor layer 16 and the n type semiconductor layer 14 that are formed on the substrate 11 by the method that adopts dry ecthing etc., what form n type contact layer 14b exposes regional 14d (with reference to Fig. 2 and Fig. 3).
Then,, expose on the regional 14d, for example, can form the negative pole 19 of 4 layers of structure from exposing each material that regional 14d face side stacks gradually Ni, Al, Ti and Au at this by adopting existing known method.
Then, for as mentioned above by laminated semiconductor 10 being provided with the wafer of light transmission positive pole 17, positive terminal pad 18 and negative pole 19, the back side of substrate 11 carried out grinding and grinding and after forming the mirror-like face, cut into for example square square of 350 μ m, can form light-emitting element chip (light-emitting component 1).
Manufacture method according to the III group-III nitride semiconductor light-emitting component of the present embodiment of above explanation, employing sputtering methods etc. are by the method for plasma with the raw material activation, on substrate 11, form intermediate layer 12 with single crystal organization, and, will be defined in above-mentioned scope as the dividing potential drop of the nitrogen of V group element.Thus, can form the intermediate layer 12 that constitutes by the crystalline film that has good uniformity with the short time, simultaneously for any substrate, intermediate layer 12 is become have specific anisotropic alignment films and on substrate 11 film forming.And,, can prevent that therefore the impurity of attachment in the stove etc. from sneaking in the film because the film forming speed in intermediate layer 12 improves.In addition, owing to be single crystal organization with intermediate layer 12 film forming, so intermediate layer 12 plays a role effectively as resilient coating, and therefore, the film forming half storey body layer 20 that is formed by the III group-III nitride semiconductor thereon becomes and has good crystalline crystalline film.
Therefore, can on substrate, grow intermediate layer 12 that forms by the good III group-III nitride compound of crystallinity and the semiconductor layer 20 that forms by the III group-III nitride semiconductor efficiently, the productivity ratio excellence, the III group-III nitride semiconductor light-emitting component 1 that can obtain cheapness and have the excellent characteristics of luminescence.
[lamp]
Can adopt the known means of those skilled in the art to constitute lamp by with III group-III nitride semiconductor light-emitting component that the present invention relates to as described above and fluorophor combination.Made up the technology that changes illuminant colour with regard to known by light-emitting component and fluorophor in the past, can be without any restrictedly using such technology.
For example, by suitable selected fluorophor, can access than the light-emitting component ripple long luminously, in addition, the emission wavelength by making light-emitting component itself and by the wavelength mixing of fluorophor conversion can be made the alight that is white in color.
In addition, as lamp, can be used for general purpose bullet cut, make in any purposes of lateral emitting (side-view) type of the purposes backlight of the formula of taking, end face luminous (top-view) type that display uses etc.
For example, example as shown in Figure 4, to be assembled into the occasion of bullet cut with the III group-III nitride semiconductor light-emitting component of an electrode type, one among light-emitting component 1 and 2 frames (being frame 31 in Fig. 4) engaged, in addition, engage with frame 32 by the negative pole (with reference to the label of representing among Fig. 3 19) of line 34, engage with frame 31 by the positive terminal pad (with reference to the label of representing among Fig. 3 18) of line 33 with light-emitting component 1 with light-emitting component 1.Then, by the periphery of the mold 35 molding light-emitting components 1 that form by transparent resin, can make the lamp 3 of bullet cut as shown in Figure 4.
In addition, the III group-III nitride compound laminated semiconductor that the present invention relates to except above-mentioned light-emitting component, can also be used for the components of photo-electric conversion of laser diode, photo detector etc. or the electronic device of HBT, HEMT etc. etc.These semiconductor elements, the semiconductor element of known various structures, stacked semiconductor component structure on the basalis 14a that sends out element 1 of present embodiment comprises these well-known component structures, without any restriction.
Embodiment
Illustrate in greater detail III group-III nitride semiconductor light-emitting component of the present invention by the following examples, but the present invention has more than and is limited to these embodiment.
Fig. 1 represents the cross section ideograph of the laminated semiconductor of the III group-III nitride semiconductor light-emitting component made in the present embodiment.
In this example, the layer of the single crystal organization that adopts the RF sputtering method to form on the c face of the substrate 11 that is formed by sapphire to be made of AlN is as intermediate layer 12, the employing mocvd method on this intermediate layer 12, form by GaN constitute layer as basalis 14a.
At first, will be only will the one side mirror ultrafinish to the substrate 11 of the sapphire system that can be used for epitaxially grown degree, do not carry out the preliminary treatment of wet type etc. especially and import in the sputter equipment.At this, as sputter equipment, use to have the high frequency type power supply, and have the device of position mobile mechanism in target that can make magnet.
Then, in sputter equipment, substrate 11 is heated to 500 ℃, import nitrogen with the flow of 15sccm after, indoor pressure is remained on 1.0Pa, substrate 11 sides are applied the high frequency bias of 50W, by being exposed in the nitrogen plasma, clean substrate 11 surfaces.
Then, the temperature former state of substrate 11 ground is constant, imports argon gas and nitrogen in sputter equipment.Then, metal A l target side is applied the high frequency bias of 2000W, pressure in the stove is remained on 0.5Pa, Ar gas is circulated with 5sccm, nitrogen is with under the condition of 15sccm circulation (ratio of nitrogen in gas gross is 75%), and film forming goes out the intermediate layer 12 of the monocrystalline that is formed by AlN on the substrate of being made by sapphire 11.
Magnet in the target all shakes under the arbitrary situation when washing substrate 11 and during film forming.
Then, according to the film forming speed of measuring in advance (0.067nm/ second), by the processing of official hour, film forming stops plasma work after going out the AlN (intermediate layer 12) of 40nm, and the temperature of substrate 11 is reduced.
In addition, sputtering time is fixed, under the condition of following six levels, promptly, in the condition (nitrogen is 0% with respect to the ratio of gas gross) that makes argon gas with the 20sccm circulation, the condition (nitrogen is 20% with respect to the ratio of gas gross) that argon gas is circulated with 4sccm with 16sccm circulation and nitrogen, the condition (nitrogen is 40% with respect to the ratio of gas gross) that argon gas is circulated with 8sccm with 12sccm circulation and nitrogen, the condition (nitrogen is 60% with respect to the ratio of gas gross) that argon gas is circulated with 12sccm with 8sccm circulation and nitrogen, the condition (nitrogen is 80% with respect to the ratio of gas gross) that argon gas is circulated with 16sccm with 4sccm circulation and nitrogen, only make under the condition (nitrogen is 100% with respect to the ratio of gas gross) of nitrogen with the 20sccm circulation, carry out and above-mentioned same operation, manufactured experimently the sample that on the substrate of being made by sapphire film forming goes out the intermediate layer that is formed by AlN.Magnet in the target all shakes under any situation when washing substrate 11 and during film forming.
Then, the film forming speed according to measuring in advance carries out the processing of official hour, and film forming stops plasma work after going out the AlN (intermediate layer) of 40nm, and the temperature of substrate is reduced.
Then, from sputter equipment, take out the substrate 11 that film forming has intermediate layer 12, import in the MOCVD stove.In addition, adopt mocvd method by following sequentially built film forming the sample of GaN layer (III group-III nitride semiconductor) is arranged.
At first, substrate 11 is imported in the reacting furnace.In the spherical case of being crossed by nitrogen replacement, substrate 11 is positioned on the receptor (suscepter) of the carbon system that heats usefulness.Then, nitrogen is circulated in stove after, make the temperature of substrate 11 be warmed up to 1150 ℃ by heater.Affirmation substrate 11 is opened the valve of ammonia pipe arrangement behind 1150 ℃ temperature stabilization, the circulation of beginning ammonia in stove.Then, in stove, supply with the hydrogen that contains trimethyl gallium (TMG) steam, make film forming on the intermediate layer on the substrate 11 12, adhere to the processing of the GaN based semiconductor that constitutes basalis 14a.The amount of ammonia is regulated so that the V/III ratio is 6000.Approximately, switch the valve of the pipe arrangement of TMG, stop the supply of raw material in reacting furnace, growth is stopped through after the growth of carrying out above-mentioned GaN based semiconductor in 1 hour.Then, make the growth ending of GaN based semiconductor after, stop heater energising, the temperature of substrate 11 is dropped to room temperature.
By above operation, make following sample, described sample is on the substrate of being made by sapphire 11, forms the intermediate layer 12 of the monocrystalline that is made of AlN, and then has formed the sample of the basalis 14a that is formed by the GaN based semiconductor of the thickness 2 μ m of non-doping on this intermediate layer 12.
Then, adopt the X ray swing curve (XRC) of GaN layer (basalis) of the non-doping of said method growth to measure.This measure to use Cu β ray X ray the source to take place as light source, utilizes as (0002) face of oriented surface with as (10-10) face of vertical plane and carries out.
Usually, in the occasion that is the III group-III nitride semiconductor, the wide index that becomes the flatness (mosaicity) of crystallization of the XRC spectrum half value of (0002) face, (10-10) the wide index that becomes the dislocation density (twist) of crystallization of the XRC spectrum half value of face.
In the curve of Fig. 6 and table 1, express with above-mentioned each nitrogen concentration make the intermediate layer growth, the half value of the X ray swing curve (XRC) of the non-Doped GaN layer (basalis) of film forming is wide on this intermediate layer.
Table 1
Figure A20078004401800321
Shown in Fig. 6 and table 1, making nitrogen concentration is 40%, adopt sputtering method film forming on substrate to go out the occasion in the intermediate layer that constitutes by AlN, on this intermediate layer the XRC spectrum half value of (0002) face of the non-Doped GaN layer of film forming wide be 132.8 arcseconds (arcsec), (10-10) the XRC spectrum half value of face is wide is 331.4 arcseconds, can confirm that equal crystallinity is good, the surface is mirror-like.In this example, at nitrogen concentration is the occasion that 60～80% scope forms the intermediate layer, the crystallinity of the non-Doped GaN layer of film forming is good on this intermediate layer, especially be 80% to form the occasion in intermediate layer at nitrogen concentration, on this intermediate layer the XRC spectrum half value of (0002) face of the non-Doped GaN layer of film forming wide be 77.8 arcseconds, (10-10) the XRC spectrum half value of face is wide is 218.8 arcseconds, shows it is best nitrogen concentration.
Relative therewith, making nitrogen concentration is the occasion that forms the intermediate layer below 20%, and when AlN was carried out sputter, Al was with the metallic state film forming on substrate, and the surface in intermediate layer is the state of gonorrhoea, can not measure X ray swing curve (XRC).
Show by above result, the III group-III nitride semiconductor light-emitting component productivity ratio excellence that the present invention relates to, and have the excellent characteristics of luminescence.
Utilize possibility on the industry
The III group-III nitride semiconductor light-emitting component that the present invention relates to has by having good crystallinity The superficial layer that consists of of III group-III nitride semiconductor crystallization. Therefore, by further forming tool thereon The III group-III nitride semiconductor crystallizing layer that function is arranged can be made and has the luminous of the excellent characteristics of luminescence The semiconductor light-emitting elements of diode (LED), laser diode (LD) or electronic device etc.
Among the present invention the expression number range " more than " and " following " include given figure.

Claims (22)

1, a kind of manufacture method of III group-III nitride semiconductor light-emitting component, be to make its reaction by the gas and the metal material activation that will contain V group element by plasma, thereby film forming goes out the intermediate layer that is formed by III group-III nitride compound on substrate, on this intermediate layer, stack gradually the n type semiconductor layer that forms by the III group-III nitride semiconductor, the manufacture method of the III group-III nitride semiconductor light-emitting component of luminescent layer and p type semiconductor layer, it is characterized in that, described V group element is a nitrogen, the gas branch rate of the nitrogen in the described gas when forming described intermediate layer is greater than 20% and in the scope below 99%, and forms described intermediate layer as single crystal organization.
2, the manufacture method of III group-III nitride semiconductor light-emitting component according to claim 1 is characterized in that, adopts sputtering method to form described intermediate layer.
3, the manufacture method of III group-III nitride semiconductor light-emitting component according to claim 2 is characterized in that, adopts the RF sputtering method to form described intermediate layer.
4, the manufacture method of III group-III nitride semiconductor light-emitting component according to claim 3 is characterized in that, forms described intermediate layer while adopt the RF sputtering method that the magnet of negative electrode is moved.
5, the manufacture method of III group-III nitride semiconductor light-emitting component according to claim 2 is characterized in that, adopts the reactive sputtering that the gas that contains V group element is circulated in reactor to form described intermediate layer.
6, the manufacture method of III group-III nitride semiconductor light-emitting component according to claim 1 is characterized in that, described metal material is the material that contains Al.
7, the manufacture method of III group-III nitride semiconductor light-emitting component according to claim 1 is characterized in that, the temperature that makes described substrate is that the scope of room temperature～1000 ℃ forms described intermediate layer.
8, the manufacture method of III group-III nitride semiconductor light-emitting component according to claim 1 is characterized in that, the basalis that stacked described n type semiconductor layer is had on described intermediate layer.
9, the manufacture method of III group-III nitride semiconductor light-emitting component according to claim 8 is characterized in that, forms described basalis by the GaN based compound semiconductor.
10, the manufacture method of III group-III nitride semiconductor light-emitting component according to claim 8 is characterized in that, forms described intermediate layer and described basalis respectively by different III group-III nitride compounds.
11, the manufacture method of III group-III nitride semiconductor light-emitting component according to claim 8 is characterized in that, adopts the M0CVD method to form described basalis on described intermediate layer.
12, the manufacture method of III group-III nitride semiconductor light-emitting component according to claim 8 is characterized in that, the temperature of described substrate is more than 800 ℃ when making described basalis carry out film forming.
13, a kind of III group-III nitride semiconductor light-emitting component, be to react by the gas and the metal material activation that will contain V group element by plasma, thereby film forming goes out the intermediate layer that is formed by III group-III nitride compound on substrate, on this intermediate layer, stack gradually the n type semiconductor layer that forms by the III group-III nitride semiconductor, the III group-III nitride semiconductor light-emitting component that luminescent layer and p type semiconductor layer form, it is characterized in that, described intermediate layer is that to make described V group element be nitrogen, the gas branch rate that makes the nitrogen in the described gas is for greater than 20% and the layer that goes out in the scope film forming below 99%, and is single crystal organization.
14, III group-III nitride semiconductor light-emitting component according to claim 13 is characterized in that, described intermediate layer is the composition that contains Al.
15, III group-III nitride semiconductor light-emitting component according to claim 13 is characterized in that, described intermediate layer forms in the mode more than 90% that covers described substrate surface at least.
16, III group-III nitride semiconductor light-emitting component according to claim 13 is characterized in that, described intermediate layer forms in the mode of the side that covers described substrate at least.
17, III group-III nitride semiconductor light-emitting component according to claim 13 is characterized in that, described intermediate layer forms with the side that covers described substrate and the mode at the back side.
18, III group-III nitride semiconductor light-emitting component according to claim 13 is characterized in that described intermediate layer is made of monocrystalline.
19, III group-III nitride semiconductor light-emitting component according to claim 13 is characterized in that, the thickness in described intermediate layer is the scope of 20～80nm.
20, III group-III nitride semiconductor light-emitting component according to claim 13 is characterized in that, the basalis that described n type semiconductor layer is had is stacked on described intermediate layer.
21, III group-III nitride semiconductor light-emitting component according to claim 20 is characterized in that described basalis is formed by the GaN based compound semiconductor.
22, a kind of lamp, it has used the described III group-III nitride semiconductor of claim 13 light-emitting component.
CN 200780044018 2006-12-20 2007-12-05 Method for manufacturing group iii nitride semiconductor light-emitting device, group iii nitride semiconductor light-emitting device, and lamp Pending CN101542756A (en)

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