CN100524860C - Semiconductor device and method for manufacturing the same - Google Patents
Semiconductor device and method for manufacturing the same Download PDFInfo
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- CN100524860C CN100524860C CNB2006800112180A CN200680011218A CN100524860C CN 100524860 C CN100524860 C CN 100524860C CN B2006800112180 A CNB2006800112180 A CN B2006800112180A CN 200680011218 A CN200680011218 A CN 200680011218A CN 100524860 C CN100524860 C CN 100524860C
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- 238000003475 lamination Methods 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 238000002844 melting Methods 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 2
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- 238000000576 coating method Methods 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
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- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 3
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
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Abstract
The purpose of the present invention is to provide a semiconductor element comprising an n-type gallium nitride-based compound semiconductor and a novel electrode that makes ohmic contact with the semiconductor. The semiconductor element of the present invention has an n-type gallium nitride-based compound semiconductor and an electrode forming an ohmic contact with the semiconductor, wherein the electrode has a TiW alloy layer to be in contact with the semiconductor. According to a preferred embodiment, the above-mentioned electrodes may also be used as contact electrodes. According to a preferred embodiment, the above-mentioned electrode has excellent thermal resistance. Furthermore, a method for producing the semiconductor component is proposed.
Description
Technical field
The present invention relates to a kind of semiconductor element and manufacture method thereof, described semiconductor element comprises n type gallium nitride-based compound semiconductor and carries out the electrode of ohmic contact with described semiconductor.
Background technology
Gallium nitride-based compound semiconductor (being also referred to as " GaN base semiconductor " hereinafter) is a kind of compound semiconductor that constitutes by the III group-III nitride of following chemical formulation:
Al
aIn
bGa
1-a-bN(0≤a≤1，0≤b≤1，0≤a+b≤1)，
Described GaN base semiconductor is by having these compounds such as GaN, InGaN, AlGaN, AlInGaN, AlN, InN etc. as example.In the compound semiconductor of above-mentioned chemical formula, a part of III family element waited with B (boron), Tl (thallium) replace, wait the compound that replaces to be also contained in the GaN base semiconductor with P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth) a part of N (nitrogen).
In recent years, the GaN based semiconductor light-emitting element such as light-emitting diode (LED), laser diode (LD) etc. of emission with the light from the green glow to the ultraviolet wavelength put into practice and caused attention.This light-emitting component has by pn junction diode structure that n type GaN base semiconductor and p type GaN base semiconductor are connected to form as basic system.Briefly, according to the luminous mechanism of light-emitting component, the electronics in being injected into n type GaN base semiconductor and be injected in the p type GaN base semiconductor positive hole pn knot and near when engaging degradedness once more, launch and the corresponding light of described energy.In this element, will be used for electrode is injected into n type GaN base semiconductor effectively with the electrode (being also referred to as " n type Ohmic electrode " hereinafter) that n type GaN base semiconductor carries out ohmic contact.In LED, generally adopt n type Ohmic electrode wherein also as the structure of contact electrode.Contact electrode is the electrode that the bonding wire that is electrically connected of a kind of outer electrode that will be used for element and element, scolder etc. are engaged.Require contact electrode to show and bonding wire (for example Au line) or the good zygosity of scolder (for example Au-Sn is total to solution).When zygosity is more weak, may in the chip mounting process defective appear.
Traditionally, used Al (aluminium) monofilm or wherein aluminium lamination has been laminated to multilayer film on Ti (titanium) layer as n type Ohmic electrode (JP-A-7-45867, USP 5,563,422).Yet because these electrodes mainly are made of aluminium lamination, they show lower thermal resistance, for example may be easily deformable when applying heat treatment.This is caused by the following fact: aluminium has than low melting point, because compare the thermal coefficient of expansion of aluminium with GaN base semiconductor etc. quite big, thermal stress is easy to develop into electrode interior.In addition, when using these electrodes as contact electrode, form oxide-film on the surface of aluminium, this makes by Au-Sn eutectic scolder the degenerated zygosity and the wetability of Au line.Therefore, output is tended to lower in the chip installation process.In order to address this problem, advised a kind of electrode (JP-A-7-221103, USP 5,563,422), wherein on by Al layer with layer place that suitable high-melting point metal constitutes lamination the Au layer.Yet this electrode also requires heat treatment under about 400 ℃ temperature to reduce contact resistance, because this electrode contacts with n type GaN base semiconductor at Al layer place.Heat treatment makes electrode surface coarse, and may degeneration and the zygosity of closing line or scolder.This electrode is associated with the problem that is difficult to produce the same nature with good reproducibility because since the disperse state of the Al that causes of thermal stress and Au influence heat treatment afterwards with the contact resistance of n type GaN base semiconductor.
As the n type Ohmic electrode that does not contain Al, JP-A-11-8410 discloses to be provided by lamination TiW alloy-layer, Ge (germanium) layer and Rh (rhodium) layer and by lamination being heat-treated the n type Ohmic electrode that obtains.By forming the principle that good ohmic contacts with the electrode of n type GaN base semiconductor is unclear.Yet,, suppose that the product that is produced by the chemical reaction that comprises whole three kinds of metal levels plays certain effect because form good Ohmic contact with the lamination sequence independence ground of these three metal levels.Unless expectation subsequently heat treated condition under with this three adjusting of pressing layer by layer and when strictly being controlled at electrode formation thus, otherwise can not stablize the character of the electrode that obtains.Therefore, think and use the semiconductor element of this electrode not to be suitable for large-scale production.
Summary of the invention
Realized the present invention under the circumstances, and aimed to provide the semiconductor element that comprises novel Ohmic electrode that described Ohmic electrode and n type GaN base semiconductor form good Ohmic contact.The present invention also aims to provide a kind of semiconductor element of the n of comprising type Ohmic electrode, preferably, can described n type Ohmic electrode as contact electrode.In addition, the present invention aims to provide a kind of semiconductor element that comprises the n type Ohmic electrode of thermal resistance excellence.In addition, the present invention aims to provide a kind of production method of above-mentioned semiconductor element.
Feature of the present invention is as follows.
(1) comprise the semiconductor element of n type gallium nitride-based compound semiconductor, and with the electrode of described semiconductor ohmic contact, wherein said electrode has the TiW alloy-layer that contacts with described semiconductor.
(2) semiconductor element of above (1), wherein said TiW alloy-layer has the Ti concentration smaller or equal to 70wt%.
(3) semiconductor element of above (2), wherein said TiW alloy-layer has the Ti concentration smaller or equal to 40wt%.
(4) semiconductor element of above (3), wherein said TiW alloy-layer has the Ti concentration smaller or equal to 8wt%.
(5) any semiconductor element of above (1)-(4), wherein said TiW alloy-layer has the Ti concentration more than or equal to 4wt%.
(6) semiconductor element of above (1), wherein along the thickness direction of TiW alloy-layer, the W-Ti composition of described TiW alloy-layer is more constant than in fact.
(7) semiconductor element of above (1) wherein forms the TiW alloy-layer by using Ti content to carry out sputter smaller or equal to the Ti-W target of 90wt%.
(8) semiconductor element of above (1) wherein forms the TiW alloy-layer by using Ti content to carry out sputter as the Ti-W target of 10wt%.
(9) semiconductor element of above (4) or (8), wherein said electrode is heat treated.
(10) semiconductor element of any of above (1) to (9), wherein said electrode has the metal level of lamination on the TiW alloy-layer.
(11) semiconductor element of above (10), wherein said metal level comprises the Au layer.
(12) semiconductor element of above (11), wherein said layer are included in the gold layer of contact laminating on the above-mentioned TiW alloy-layer.
(13) semiconductor element of above (11), wherein said metal level is made of the individual layer of Au, perhaps constitutes by having the lamination lamination of Au layer as top layer.
(14) semiconductor element of above (11), wherein said metal level include only has identical fusing point with Au or than Au high-melting point metal more.
(15) semiconductor element of above (10), wherein said metal level does not contain Rh.
(16) above (1) to (15) any semiconductor element, wherein electrode surface has the arithmetic average roughness Ra smaller or equal to 0.02 micron.
(17) be used to produce the method for semiconductor element, described method comprises: form the step of TiW alloy-layer as the part of the lip-deep electrode of n type gallium nitride-based compound semiconductor.
(18) production method of above (17) wherein forms the TiW alloy-layer by using the Ti-W target to carry out sputter.
(19) production method of above (18), wherein said TiW alloy-layer has the Ti concentration smaller or equal to 70wt%.
(20) production method of above (18), described method also comprises: to TiW alloy-layer step of heat treatment.
In the present invention, described TiW alloy in fact only is made up of Ti and W (tungsten).According to the present invention, can obtain to comprise the semiconductor element of n type Ohmic electrode, described n type Ohmic electrode forms and contacts with the good ohmic of n type GaN base semiconductor.According to a preferred embodiment of the invention, can obtain to comprise the semiconductor element of n type Ohmic electrode, preferably use described n type Ohmic electrode as contact electrode.According to a preferred embodiment of the invention, can obtain to comprise the thermal resistance semiconductor element of n type Ohmic electrode preferably.
Description of drawings
Fig. 1 is the schematic diagram of the structure of embodiment of the invention gallium nitride-based compound semiconductor element, and Fig. 1 (a) is a top view, and Fig. 1 (b) is the profile that the X-Y line along Fig. 1 (a) obtains.
Fig. 2 shows the observation image of the electrode surface of differential interference microscope.
Fig. 3 shows by the constituent analysis result of auger electron spectroscopy along electrode direction.
Fig. 4 shows the observation image by the electrode surface of differential interference microscope.
Fig. 5 shows the observation image by the electrode surface of differential interference microscope.
Fig. 6 shows by the constituent analysis result of Auger electrode spectrum along the electrode depth direction.
The meaning of symbol is as follows among Fig. 1:
1 substrate, 2 first resilient coatings, 3 second resilient coatings, 4n type contact layer, 5 active layers, 6p type covering, 7p type contact layer, P1n lateral electrode, P2p lateral electrode, P21p side Ohmic electrode, P22p side engagement electrode, 100 semiconductor elements.
Embodiment
The present invention can be applied to comprise any element of n type GaN base semiconductor and electrode, and described electrode forms and semi-conductive ohmic contact, i.e. n type Ohmic electrode.Semiconductor element of the present invention comprises the part that the semiconductor except the GaN base semiconductor constitutes.Typically, semiconductor element of the present invention is a light-emitting component.Alternatively, for example described semiconductor element can be light receiving element or the electronic component that injects transistor and so on.
In semiconductor element of the present invention, the n type GaN base semiconductor that forms n type Ohmic electrode on it can have any composition.N type GaN base semiconductor can be non-doping or be doped with impurity, as long as it shows n type conductivity.Preferably, the n type GaN base semiconductor that contacts with the TiW alloy-layer is Al
xGa
1-xN (0≤x≤0.2).In addition, preferably, the n type GaN base semiconductor that contacts with the TiW alloy-layer has 1 * 10
18/ cm
3～1 * 10
20/ cm
3Carrier concentration, preferably 5 * 10
18/ cm
3～5 * 10
19/ cm
3Carrier concentration.Particularly, it is preferred having the n type GaN base semiconductor that is in the carrier concentration of above-mentioned preferred concentration range for by the Doped n-type Control of Impurities.Such n type impurity without limits, and any known n type impurity such as Si, Ge etc. can be applicable to the GaN base semiconductor.In semiconductor element of the present invention, can be by such as MOVPE (metal organic chemical vapor deposition), HVPE (hydride vapour deposition), MBE formation such as (molecular beam epitaxies) or formed the n type GaN base semiconductor of n type Ohmic electrode on it by formation such as high pressure method, liquid phase process.N type GaN base semiconductor can be produced as the film on the substrate, perhaps can be substrate.
In semiconductor element of the present invention, n type Ohmic electrode is also as contact electrode.Alternatively, except n type Ohmic electrode, semiconductor element can have the one or more contact electrodes that are electrically connected with n type Ohmic electrode.When n type Ohmic electrode also when the contact electrode, have specific surface more the electrode of high flat degree show the better engagement state of electrode and closing line or scolder, this use automaton has improved the output in the joint technology.Particularly, also as the arithmetic average roughness Ra of the n type surface ohmic electrode of contact electrode preferably smaller or equal to 0.02 micron.
For semiconductor element of the present invention, the method that forms the TiW alloy-layer that comprises in the n type Ohmic electrode and can suitably be used the conventional known method that forms the TiW alloy firm without limits.Preferably, can form the TiW alloy-layer by using sputter.Can be according to JP-A-5-295531 (USP5,470,527), JP-A-4-193947, JP-A-4-293770 (USP 5,160,534) and the gas known technology details of Ti-W target as can be known.Except Ti and W, the TiW alloy-layer that uses the Ti-W target to form may comprise the impurity that is included in inevitably in the target.It is acceptable that the TiW alloy-layer comprises this impurity that is difficult to remove from the beginning material.In semiconductor element of the present invention, the thickness of the TiW alloy that comprises in n type Ohmic electrode for example is 0.01 micron to 1 micron, preferably, is 0.05 micron to 0.5 micron.The Ti concentration of TiW alloy-layer does not have concrete restriction.Yet, when the 5wt% of the Ti content in the Ti-W target during, a little less than the TiW alloy firm of formation and the adhesiveness between the substrate become, and it is said that described film is easy to separate (USP5,470,527) from substrate less than situation about forming by sputter.When the Ti of Ti-W target content during less than 5wt%, the TiW alloy-layer of formation has the Ti concentration less than 4wt%, and therefore preferably, the TiW alloy-layer has the Ti concentration that is not less than 4wt%.As shown in the following experimental example, when the TiW alloy-layer in the electrode had lower Ti concentration, the thermal resistance of n type Ohmic electrode became better.Therefore, preferentially, the Ti concentration of TiW alloy-layer is smaller or equal to 40wt%, more preferably, and smaller or equal to 20wt%, more preferably, smaller or equal to 8wt%.
In the TiW alloy-layer, preferably, the composition of W and Ti is than constant along the thickness direction essence of described layer.When the composition of W and Ti when constant, in default of density gradient, the diffusion of W atom and Ti atom can not take place.Therefore, when being placed on semiconductor element in the hot environment, the known change of properties of n type Ohmic electrode.
In semiconductor element of the present invention, n type Ohmic electrode can be by TiW alloy-layer that contacts with n type GaN base semiconductor and the lamination lamination that the metal level of lamination constitutes on the TiW alloy-layer.Metal level can be formed by any metal material (can be independent metal or alloy).In addition, metal level can be independent layer or have laminar structure.In order to reduce the impedance of electrode, preferably, metal level is formed by the metal with high conductivity, for example Ag, Cu, Au, Al etc.When being formed according to this lamination, n type Ohmic electrode, preferably, metal level is formed the lamination lamination of Au layer or Au layer and other metal levels in order to reduce to be applied to the thermal stress on the TiW alloy-layer.This is because Au is softer and is easily deformable metal.By reducing to be applied to the thermal stress on the TiW alloy-layer, can prevent such as distortion and n type Ohmic electrode separates and n type Ohmic electrode and n type GaN base semiconductor between the contact unsteadiness problem take place.Think that this effect is significant especially when being laminated directly to the Au layer on the TiW alloy-layer.When n type Ohmic electrode is above-mentioned lamination lamination, the layer that on the surface of lamination lamination, exposes, promptly the top layer of the metal level of lamination is made up of the chemically stable metal such as Au, platinum family element etc. on the TiW alloy-layer, thereby has improved the resistance that corrodes for n type Ohmic electrode.When n type Ohmic electrode also was used as contact electrode, preferably, top layer was the Au layer.When n type Ohmic electrode is an above-mentioned lamination lamination and will be laminated to metal level on the TiW alloy-layer and comprise the Al layer time, described electrode shows the thermal resistance of degeneration.Therefore, from the aspect of thermal resistance, preferably metal level does not comprise Al.When the metal level that will comprise the Au layer is laminated on the TiW alloy-layer, consider thermal resistance, preferably form to include only and have identical fusing point or than Au high-melting point metal layer more with Au.
Ohmic contact between n type ohm motor in semiconductor element of the present invention and the n type GaN base semiconductor is not that the reaction by the product of the chemical reaction that comprises Rh produces, with different at the disclosed electrode of JP-A-11-8410.Therefore, when the n type Ohmic electrode in semiconductor element of the present invention was above-mentioned lamination lamination, the metal level that will be laminated to the TiW alloy-layer can be not contain Rh.
In semiconductor element of the present invention, can omit the heat treatment of n type Ohmic electrode.This is because show the contact impedance that can not cause the reduced levels of practical problem at TiW alloy-layer place with the n type Ohmic electrode that n type GaN base semiconductor contacts, even need not heat treatment.In the time can omitting the heat treatment of n type Ohmic electrode, the advantage that provides is: can shorten and produce the required time, and can increase the degree of freedom of the production technology design of semiconductor element.In addition, when omitting heat treatment, solved because the problem of the electrode surface roughening that heat treatment causes by himself.Therefore, n type Ohmic electrode is applicable to same electrode as contact electrode.
On the other hand, in semiconductor element of the present invention, can at random carry out the heat treatment of n type Ohmic electrode.The required character of short of weakening, the thermal resistance that can depend on electrode is suitably set heat treated temperature and time.As being used for heat treated atmosphere gas, preferably, use the inert gas such as nitrogen, rare gas etc.When n type Ohmic electrode is above-mentioned lamination lamination, can after the formation of finishing the lamination lamination, apply described heat treatment.Alternatively, apply described heat treatment in the time of for example can working as formation TiW alloy-layer, and metal level can be laminated on the TiW alloy-layer subsequently.When heat treatment being applied to n type Ohmic electrode, the composition that n type GaN base semiconductor may take place is diffused in the TiW alloy-layer or the composition of TiW alloy is diffused in the n type GaN base semiconductor.Yet, short of weakening effect of the present invention, this diffusion is acceptable.
Example
Below will explain the present invention in detail by reference example, described example is not to be restrictive.
＜experimental example 1, (example 1, comparative example 1) 〉
Preparation has the GaN based semiconductor component of structure as shown in Figure 1 and it is assessed.GaN based semiconductor component 100 shown in Fig. 1 is the light-emitting diodes with following structure: first resilient coating 2, second resilient coating 3, n type contact layer 4, active layer 5, p type cap rock 6 and p type contact layer 7 are pressed onto on the substrate 1 by this sequential layer.On n type contact layer 4, formed the n lateral electrode P1 that carries out ohmic contact with n type contact layer 4.On p type contact layer 7, formed the p lateral electrode P2 that carries out ohmic contact with p type contact layer 7.The P lateral electrode is made up of the p side Ohmic electrode P21 that forms on the whole surface of p type contact layer 7, and p side engagement electrode P22 is electrically connected with p side Ohmic electrode P21.GaN based semiconductor component 100 is prepared as follows.
(crystal growth)
Sapphire Substrate 1 (2 inches diameter) is arranged in the MOVPE growth furnace, in flowing hydrogen, underlayer temperature is elevated to 1100 ℃, thus the surface of clean substrate 1.Then, underlayer temperature is dropped to 500 ℃, and use hydrogen as carrier gas and ammonia and TMG (trimethyl gallium) as starting on substrate 1, grow first resilient coating of forming by GaN 2 of the about 30nm of thickness of beginning material gas.Then, stop the supply of TMG, and underlayer temperature is elevated to 1000 ℃.Use TMG and ammonia material gas to start with, second resilient coating 3 that the about 2 microns non-Doped GaN of growth thickness is formed.Then, additionally provide the n type contact layer 4 of silane gas, constitute to realize about 5 * 10 by the GaN of doping Si (silicon) with 3 microns of thickness of growth
18/ cm
3Concentration.Then, stop supplies TMG and silane gas are reduced to 800 ℃ with underlayer temperature, and use TMG, TMI (trimethyl indium), silane gas and ammonia, alternately grow by In
xGa
1-xBase layer and In that N forms
yGa
1-yThe trap layer that N (y〉x) forms is to form the active layer 5 that two ends have the multi-quantum pit structure of building layer.The thickness of building layer is set at 10nm, and the thickness of trap layer is set at 2nm.In addition, In component y in the trap layer is regulated to realize the excitation wavelength of 400nm.Then, stop supplies TMG, TMI and silane gas are elevated to underlayer temperature 1000 ℃ once more, use TMG, TMA (trimethyl aluminium) ammonia and (EtCp)
2Mg (dicyclopentadiene base magnesium) will have an appointment 5 * 10 by doping
19/ cm
3The Al of the Mg of concentration (magnesium)
0.1Ga
0.9The p type cap rock 6 that N constitutes is grown to thickness 30nm.Then, stop the supply of TMA, and doping is had an appointment 8 * 10
19/ cm
3The p type contact layer 7 that the GaN of the Mg of concentration constitutes is grown to thickness 120nm.After the growth of finishing p type contact layer 7, stop the substrate heating, stop the supply of the beginning material gas except ammonia, and underlayer temperature is reduced to room temperature.Thereafter, in order to activate the p type cap rock 6 of mixing Mg and to mix magnesium in the p type contact layer 7 of magnesium, the heat treatment of 900 ℃ of the execution nitrogen atmosphere in RTA equipment (rapid thermal annealing equipment) under 1 minute.
(formation of p side Ohmic electrode)
Next, form p side Ohmic electrode P21, wherein Pd layer (thickness 30nm), Au layer (thickness 100nm) and Ni layer (thickness 10nm) are pressed onto on the surface of p type contact layer 7 (wafer top layer) according to this sequential layer by electron beam evaporation.Shown in Fig. 1 (a), when p side Ohmic electrode P21 when the top is watched has the lattice pattern of quadrature.In other words, p side Ohmic electrode P21 is the opening electrode, the square openings that is provided with a large amount of through electrode films regularly along the length and the width of film wherein, and the surface of p side contact layer 7 come out from opening.Size at foursquare openings at one side is 8 microns, and is 2 microns at the distance between length and the width adjacent apertures (electrode part width).By traditional stripping means p side Ohmic electrode P21 is carried out composition.Promptly, forming by photoetching composition on the surface of p type contact layer 7 is the resist film of reservation shape, formation has the electrode film of above-mentioned laminar structure and Etching mask is peeled off on described resist film, thereby has removed the electrode film that deposits on Etching mask.Use RTA equipment, P21 heat-treats to p side Ohmic electrode.Thereafter, heat treated condition is nitrogen atmosphere, 500 ℃ and 1 minute.
(formation of n lateral electrode)
Next, formed thereon and formed Etching mask on the p type contact layer 7 of p side Ohmic electrode P21 with given shape.By using the RIE (reactive ion etching) of chlorine, from p type contact layer 7 one sides described layer is carried out etching, to expose the surface of n type contact layer 4 as shown in Figure 1.After exposing, by the RF sputter TiW alloy-layer (thickness 100nm), Au layer (thickness 100nm), Pt layer (thickness 80nm), Au layer (thickness 80nm), Pt layer (thickness 80nm), Au layer (thickness 80nm), Pt layer (thickness 80nm) and Au layer (thickness 80nm) are pressed onto on the surface of n type contact layer 4 according to this sequential layer, thereby form n lateral electrode P1.For forming the TiW alloy-layer by the RF sputter, (Mitsubishi Materials company makes, name of product: 4N W-10wt%Ti target) as target, use Ar (argon gas) as sputter gas, and adopt the RF power, 1.0 * 10 of 200W to use the Ti-W target
-1The sputtering pressure of Pa.The Ti content of Ti-W target is that the Fe (iron) of 10.16wt% (assay value that obtains by absorptionmetry) and 15ppm is as impurity (by the assay value of ICP acquisition).As the stripping means in the composition of p side Ohmic electrode P21 n lateral electrode P1 is carried out composition.
(forming p side engagement electrode)
Next, on p side Ohmic electrode P21, form p side engagement electrode P22, wherein will have the Ti of thickness 20nm and have the Au of thickness 600nm according to this order lamination by electron beam evaporation.Then, use plasma CVD, form by SiO
2The passivating film (not shown, thickness 300nm) that constitutes is to cover the wafer surface except n lateral electrode P1 and p side engagement electrode P22.Subsequently, use RTA equipment, n lateral electrode P1 and p side engagement electrode P22 are heat-treated.Heat treated condition is nitrogen atmosphere, 500 ℃ and 1 minute.In this manner, on wafer, formed 350 microns square light-emitting diode (example 1).
(assessment)
To need not element separation (being cut into chip) by the light-emitting diode that above-mentioned steps is prepared assesses as forming on wafer.Fig. 2 shows and utilizes the observation image of differential interference microscope to the surface of n lateral electrode P1.As shown in Figure 2, the surface of n lateral electrode P1 is smooth and does not have roughening.Although observed many diagonal at the center of electrode, they are cuts of the generation in the electrical properties evaluation process when contacting with the probe of autodetector, and can not show surface roughness.Vf (forward voltage) when utilizing the autodetector measurement that the forward current of 20mA is flow through in element, and find it is 3.4V.This value is the standard value as the Vf of the light-emitting diode with 400nm excitation wavelength.The contact resistance that it should be understood that n lateral electrode P1 and n type contact layer 4 thus is enough low to avoid practical problem.This also means between n lateral electrode P1 and n type contact layer 4 and has formed good Ohmic contact.The result that shown in Figure 3 is along the depth direction constituent analysis of n lateral electrode P1, described result is to use auger electron spectroscopy (AES) to obtain.According to Fig. 3, it should be understood that n lateral electrode P1 contacts at TiW alloy-layer place with n type contact layer 4.In addition, it should also be understood that the composition of Ti and W in the TiW alloy-layer is than constant along thickness direction essence.
In order to compare, prepared to have light-emitting diode (comparative example 1) with said elements (example 1) same structure by the method identical with being used for said elements, difference is that the n lateral electrode is the Al layer (thickness 600nm) that forms by electron beam evaporation.The result of example 1 element assessment as a comparison, although the Vf that utilizes autodetector to measure is identical level with the element of example 1, the roughening significantly of the surface of n lateral electrode.
＜experimental example 2 (example 2, comparative example 2) 〉
Prepared test wafer GaN resilient coating by MOVPE, wherein at Sapphire Substrate (2 inches diameter) the GaN layer of doping Si of having gone up low-temperature epitaxy.The following two types electrode of electrode A and electrode B forms on described resilient coating, and described electrode is assessed.
Electrode A: by with TiW alloy-layer (thickness 100nm) and Au layer (thickness 100nm) according to this order lamination, and apply heat treatment at 500 ℃ and formed (example 2) in 1 minute.
Electrode B: by with Al layer (thickness 100nm) and Au layer (thickness 100nm) according to this order lamination, and apply heat treatment at 400 ℃ and formed (comparative example 2) in 1 minute.
The respective metal layers that comprises in electrode A and electrode B forms by the RF sputter.Film formation condition for the TiW alloy-layer that comprises in electrode A and electrode B is identical with the condition of the TiW alloy-layer that is used for using in experimental example 1.By photoetching with peel off electrode is carried out composition.For photoetching, use the employed mask of composition of the n lateral electrode P1 in experimental example 1.
Fig. 4 shows by the observation image of differential interference microscope to the electrode A surface.In addition, Fig. 5 shows by the observation image of differential interference microscope to the surface of electrode B.As shown in Figure 4, although heat treatment is 500 ℃, being smooth and not having roughening by the surface that at first on the GaN of doping Si layer, forms the TiW alloy-layer, Au is pressed onto layer by layer the electrode A that forms on the TiW alloy-layer then. the arithmetic average roughness Ra on measurement electrode A surface and discovery are 0.014 micron. because be about 0.004 micron as the Ra of the GaN layer of the doping Si of the susceptor surface that is used for electrode formation, the Ra on electrode A surface is smaller or equal to 4 times of susceptor surface.On the contrary, as shown in Figure 5,, obviously be coarse by the surface that forms Al layer and the electrode B that lamination TiW layer and Au layer obtain on the Al layer subsequently although heat treatment temperature is 400 ℃.The arithmetic average roughness Ra on measurement electrode B surface, and find it is 0.07 micron.This is as the GaN laminar surface roughness of the doping Si of susceptor surface 18 times.
Fig. 6 shows along the result of the constituent analysis of the depth direction of electrode B, uses auger electron spectroscopy to obtain.As shown in Figure 6, in electrode B, the Au in the Au layer that forms on the TiW alloy-layer crosses the TiW alloy-layer and diffuses to Al layer one side, and with the close part of the GaN layer of doping Si in have Al and Au.Al also crosses the TiW alloy-layer and diffuses to Au layer one side.According to experimental example 2, it should be understood that the electrode A with the TiW alloy-layer that contacts with the GaN layer of doping Si shows good thermal resistance, but the electrode B with the TiW alloy-layer that does not contact with the GaN layer of doping Si shows lower thermal resistance.What think electrode B is the existence of Al layer in the electrode B than one of reason of low thermal resistance, described aluminium lamination have low melting point and with the visibly different thermal coefficient of expansion of GaN.
Known Ti concentration of being undertaken comprising in the TiW alloy firm of sputter formation by use Ti-W target is tended to the Ti content less than target, smaller or equal to 80% (JP-A-5-295531, USP5,470,527) of Ti content in the target.In above-mentioned experimental example 1 and experimental example 2,, think that Ti concentration in the TiW alloy-layer that comprises in the n type Ohmic electrode of the sample prepared is smaller or equal to 8wt% in these experimental examples because use the Ti-W target of the Ti comprise 10wt%.
＜experimental example 3 (example 3 and 4, comparative example 3 and 4) 〉
The sample that is used to assess is prepared as follows.Mode according to identical with experimental example 1 grows on the Sapphire Substrate GaN based semiconductor from first resilient coating to p type contact layer to provide the wafer of the GaN base semiconductor lamination lamination with light emitting diode construction.Next, omit the formation of p side Ohmic electrode, form the n lateral electrode.Mode according to identical with experimental example 1 (has about 5 * 10 at the n type contact layer that exposes by RIE
18/ cm
3The doping Sin type GaN of Si concentration) forms the n lateral electrode on the surface.The n lateral electrode is following four types (sample A-sample D).
Sample A: by TiW alloy-layer (thickness 100nm) and the Au layer (thickness 100nm) of lamination is formed on the TiW alloy-layer n lateral electrode (example 3).
Sample B: by W layer (thickness 100nm) and the Au layer (thickness 100nm) of lamination is formed on the W layer n lateral electrode (comparative example 3).
Sample C: by Ti layer (thickness 100nm) and the Au layer (thickness 100nm) of lamination is formed on the Ti layer n lateral electrode (comparative example 4).
Sample D: by TiW alloy-layer (thickness 100nm) and the n lateral electrode (example 4) on the TiW alloy-layer, formed according to Au layer (thickness 100nm), Pt (thickness 80nm), Au layer (thickness 80nm), Pt layer (thickness 80nm), Au layer (thickness 80nm), Pt layer (thickness 80nm) and the Au layer (thickness 80nm) of following order lamination.
Be formed on the respective metal layers that comprises in the n lateral electrode of each sample by the RF sputter.Be used in the film formation condition of the TiW alloy-layer that sample A and sample D comprise identical with the formation condition of the TiW alloy-layer that in experimental example 1, uses.Yet,, use the Ti-W target that comprises 10wt%Ti to form the TiW alloy-layer of sample A, and use the Ti-W target that comprises 90wt%Ti to form the TiW alloy-layer of sample D as in experimental example 1.Think that the Ti concentration of the TiW alloy-layer in sample D is approximately smaller or equal to 70wt%.According to the mode identical the n lateral electrode is carried out composition at any sample with experimental example 1.Use the wafer that forms the n lateral electrode in this manner as the sample that is used to assess.
(assessment before the heat treatment)
Based on flowing through the required voltage of 20mA electric current (being also referred to as " n-n voltage " hereinafter) between the n lateral electrode that makes two adjacent elements on the wafer contact impedance of the n lateral electrode of each sample is assessed.Because can to ignore ground little with the voltage drop of the electric current symbiosis of n type contact layer inside, the contact impedance between n-n voltage reflection n lateral electrode and the n type contact layer.In other words, the sample with higher n-n voltage has higher contact impedance between n lateral electrode and n type contact layer.Utilize the autodetector measurement to have the n-n voltage of each sample of the n lateral electrode that forms by sputter.The result is as follows.
Sample A:0.3V.
Sample B:0.7V.
Sample C:0.2V.
Sample D:0.3V.
The n-n voltage 0.2V equivalence that the n-n voltage of sample A and sample D is measured with the sample separation of example 1 ground in fact.Thus, it should be understood that to use to have than the Ohmic electrode that hangs down contact impedance as formed at TiW alloy-layer place and n type GaN base semiconductor electrodes in contact.Utilize the electrode surface of differential interference microscope observation sample A and sample D, and find quite smooth.
Although the electrode of sample A contacts with n type contact layer at the TiW alloy-layer place that comprises relatively low concentration (think as mentioned above and be no more than 8%) Ti, n-n voltage that it should be noted that sample A is no more than half of n-n voltage of the sample B with electrode, and described electrode contacts with n type contact layer at W layer place.This is hinting that the character of the TiW alloy-layer in the electrode of sample A is not the simple average of Ti and W character.It should also be understood that is not having under the heat treated situation, depends on the Ti concentration of TiW alloy-layer hardly at the contact impedance of TiW alloy-layer place and n type GaN base semiconductor electrodes in contact, because the n-n voltage of sample A and sample D equates.This means that this electrode has stable character and is easy to production.
(assessment after the heat treatment)
Next, make each sample under nitrogen atmosphere, carry out 500 ℃ heat treatment 1 minute.The n-n voltage of each sample is as follows after the heat treatment.
Sample A:0.2V.
Sample B:0.7V.
Sample C:2.4V.
Sample D:3.2V.
Observe heat treatment electrode surface afterwards.As a result, the electrode surface of sample A and sample B is in good situation, and is promptly smooth and do not have roughening, and the electrode surface of sample C and sample D is coarse.
It should be understood that because the not roughening of surface of electrode in sample A by heat treatment, and n-n voltage does not change in fact by heat treatment, and the TiW alloy-layer place and the n type GaN base semiconductor electrodes in contact that will form with the sputter of the Ti-W target that comprises 10wt%Ti by use have quite good thermal resistance.It should also be understood that: use this electrode that forms by sputter after the heat treatment under the condition that can be under lab adopts in 3.When applying heat treatment, stablized the structure of electrode.Therefore, can prevent when between the operating period with the basic change of described component exposure electrode property when the high temperature.
On the contrary, the electrode of the sample D that contacts with n type contact layer at the TiW alloy-layer place that the target that uses Ti content as 90wt% forms shows significantly because the n-n voltage of the increase that heat treatment causes and the surface of degeneration.This trend is general for the electrode of the sample C that contacts with n type contact layer at the Ti layer.According to these results, it should be understood that the heat-treat condition that adopts is strict for TiW alloy-layer place and the n type GaN base semiconductor electrodes in contact that the sputter at the Ti-W target that comprises 90wt%Ti by use forms in experimental example 3.
The present invention is not limited to above-mentioned example, and can make amendment according to variety of way under the situation that does not break away from main idea of the present invention.For example, in GaN based semiconductor component 100 shown in Figure 1, p side engagement electrode P22 can have the identical structure with n lateral electrode P1, can form described electrode by identical step in this case, has therefore simplified production technology.
The application is based on patent application No.2005-112610 and the 2006-31741 that Japan submits, with its full content in the lump at this as a reference.
Claims (14)
1. semiconductor element, the semiconductor element that comprises n type gallium nitride-based compound semiconductor, and with the electrode of described semiconductor ohmic contact, wherein said electrode has the TiW alloy-layer that contacts with described semiconductor, and described TiW alloy-layer has more than or equal to 4wt% and smaller or equal to the Ti concentration of 70wt%.
2. semiconductor element according to claim 1, wherein said TiW alloy-layer has the Ti concentration smaller or equal to 40wt%.
3. semiconductor element according to claim 2, wherein said TiW alloy-layer has the Ti concentration smaller or equal to 8wt%.
4. semiconductor element according to claim 1 wherein forms the TiW alloy-layer by using Ti content to carry out sputter smaller or equal to the Ti-W target of 90wt%.
5. semiconductor element according to claim 4 wherein forms the TiW alloy-layer by using Ti content to carry out sputter as the Ti-W target of 10wt%.
6. semiconductor element according to claim 1, wherein said electrode are included in the Au layer of contact laminating on the above-mentioned TiW alloy-layer.
7. semiconductor element according to claim 1, wherein said electrode have on TiW alloy-layer lamination, include only and have identical fusing point or than the Au metal level of high-melting point metal more with Au.
8. method that is used to produce semiconductor element, described method comprises: form the step of TiW alloy-layer as the part of the lip-deep electrode of n type gallium nitride-based compound semiconductor, wherein said TiW alloy-layer has more than or equal to 4wt% and smaller or equal to the Ti concentration of 70wt%.
9. production method according to claim 8 wherein forms the TiW alloy-layer by using the Ti-W target to carry out sputter.
10. production method according to claim 9, the Ti content of wherein said Ti-W target is smaller or equal to 90wt%.
11. production method according to claim 9, described method comprises: to TiW alloy-layer step of heat treatment.
12. production method according to claim 11, wherein said TiW alloy-layer has the Ti concentration smaller or equal to 8wt%.
13. production method according to claim 11, the Ti content of wherein said TiW target is smaller or equal to 10wt%.
14. production method according to claim 11, wherein after described heat treatment step, the surface of described electrode has the arithmetic average roughness Ra smaller or equal to 0.02 micron.
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