Since the III-V group-III nitride, promptly comprise gallium nitride (GaN) for example, aluminium gallium nitride alloy (GaAIN), indium gallium nitride (InGaN), and after the epitaxial layer that waits of aluminum gallium nitride indium (InAlGaN) successfully become to grow first, because it has direct energy band, bandwidth height, satisfies and close characteristics such as drift speed height, breakdown electric field height and chemical inertness, is hopeful to be used to make the electronic installation of high temperature/high-capacity and the material of electrooptical device most so become.Recently because the enhancement of the crystalline quality of the epitaxial layer of higher-doped concentration high-quality laser diode, light-emitting diode, optical detector and the microwave field effect transnistor made from III-V group-III nitride brilliant structure of heap of stone etc. so develop.
Generally speaking, the performance of III-V group-III nitride device can be subjected to the restriction of its contact resistance.Therefore, the key technology of manufacturing high-performance III-V group-III nitride device is whether to produce the high Metal Contact of reliability.With GaN is example, though existing document has pointed out that many kinds of metals can be used as its contact, titanium/aluminium (Ti/Al) is double-deck to be the most widely-used ohmic contact layer as n type GaN on having now.Yet this Ti/Al bilayer is easily oxidized, and causes the rising of ohmic contact resistance in follow-up manufacture craft with operating period.
For fear of the at high temperature easily oxidized tendency of Ti/Al bilayer, can cover above it the low-resistance gold of one deck (Au) as passivation layer (passivation) so that its surface passivation.But gold can inwardly diffuse in titanium layer, the aluminium lamination and be penetrated in the GaN layer, and causes thermal stability, reliability and the ohmic contact characteristic variation of semiconductor device.
The cutaway view of Fig. 1 shows III-V compound semiconductor light-emitting diode (the light-emitting device based on GaN; LED) 100 typical construction.
Light-emitting diode 100 have one transparent and the insulation substrate 1, it is made with for example sapphire (sapphire).This substrate 1 has one first first type surface 1a and one second first type surface 1b.The made resilient coating 2 of GaN is formed on the first first type surface 1a of substrate 1.The III-V compound semiconductor layer 3 based on GaN of n type is formed on the resilient coating 2.This n type semiconductor layer 3 is mixed with for example germanium (Ge), selenium (Se), sulphur (S) or tellurium n type admixtures such as (Te).In addition, this n type semiconductor layer 3 can doped silicon (Si).
N type AlGaN layer 4 is formed on the n type semiconductor layer 3.Active layers 5 is formed on the n type AlGaN layer 4, and this active layers 5 is by the multiple quantum trap (MQW) that for example InGaN/GaN constituted, single quantum well (SQW) or two heterogeneous (DH) structure.P type AlGaN layer 6 is formed on the active layers 5.
The III-V compound semiconductor layer 7 based on GaN of one P type is formed on the p type AlGaN layer 6.This p type semiconductor layer 7 is mixed with p type admixtures such as for example beryllium (Be), strontium (Sr), barium (Ba), zinc (Zn) or magnesium.
As shown in Figure 1, light-emitting diode 100 has an electrode 8A and is formed on the n type semiconductor layer 3; Be formed on the p type semiconductor layer 7 with an electrode 8B.The existing electrode 8A metal materials such as titanium, aluminium, gold that comprise as indicated above.Electrode 8B is a kind of Ohmic electrode, and it can comprise for example metal materials such as nickel (Ni), chromium (Cr), gold, platinum (Pt) or titanium.
Then, with reference to the manufacturing process steps of the existing light-emitting diode 100 of the flowchart text of figure 2.
At first, shown in step 201, with resilient coating 2, n type semiconductor layer 3, n type AlGaN layer 4, active layers 5, p type AlGaN layer 6, be formed on substrate 1 top in regular turn with p type semiconductor layer 7.
Then, shown in step 202, heat-treat with activation p type AlGaN layer 6 and p type semiconductor layer 7.Because the magnesium that is mixed in p type AlGaN layer 6 and the p type semiconductor layer 7 can form the Mg-H bond, and causes the hole can't be provided.Be in this purpose of heat-treating and interrupt this Mg-H bond and activate p type AlGaN layer 6 and p type semiconductor layer 7.This heat treated condition is generally at 650 to 780 ℃ and heated 15 to 60 minutes down.
Then, shown in step 203, with p type semiconductor layer 7, p type AlGaN layer 6, active layers 5, and n type AlGaN layer 4 partially-etched removing, so that the surface of n type semiconductor layer 3 is exposed.At this, the surperficial part of n type semiconductor layer 3 is also etched to be removed.
Afterwards, shown in step 204, form electrode 8A and 8B, wherein electrode 8A is formed on the n type semiconductor layer 3, and electrode 8B is formed on the p type semiconductor layer 7.The formation of electrode 8A and 8B can utilize existing deposition technique, for example vapour deposition method or sputtering method etc.
Then, (annealing) manufacture craft of shown in step 205, annealing.The purpose of this step is for reducing the ohmic contact resistance of electrode 8A and 8B.The condition of this annealing manufacture craft is generally at 300 to 400 ℃ carries out.
Electrode 8A and 8B also can form as time as described in the step 204, after for example, also can forming electrode 8A earlier, annealing, just form electrode 8B.
Among the present invention, the nitride-based semiconductor that " based on the III-V compound semiconductor of gallium nitride " speech means the III family element that comprises gallium is GaN, GaAlN, InGaN or InAlGaN etc. for example.
Describe the present invention in detail below with reference to accompanying drawing.
The present invention proposes the structure of a kind of electrode 8A, and it comprises: an ohmic contact layer comprises for example alloy of titanium nitride, titanium, aluminium, chromium, indium, palladium or above-mentioned metal; One barrier layer is positioned at this ohmic contact layer top, and this barrier layer comprises for example platinum, tungsten (W) or nickel; Be positioned at this barrier layer top with a weld pad (pad) layer, this soldering pad layer comprises for example gold.Electrode 8A of the present invention inwardly spreads and the phenomenon that is penetrated into semiconductor device inside so can prevent the existing gold of going up soldering pad layer owing to having barrier layer.
With reference to figure 3, it shows an example of the structure of electrode 8A of the present invention.In Fig. 3, indicate with identical reference number with Fig. 1 identical construction.As shown in Figure 3, the made resilient coating 2 of GaN is formed on the substrate 1.N type semiconductor layer 3 is formed on the resilient coating 2.This n type semiconductor layer 3 can doped silicon.Electrode 8A is formed on this n type semiconductor layer 3.Electrode 8A comprises that titanium layer 81, aluminium lamination 82 are formed on the titanium layer 81, platinum layer 83 is formed on the aluminium lamination 82 and gold layer 84 is formed on the platinum layer 83.To be the advantageous property of example explanation below with this electrode 8A (Ti/Al/Pt/Au) as the ohmic contact of n type GaN.Example one
On sapphire substrate, at 520 ℃ of thick GaN resilient coatings of one deck 300nm of growing down.Then, by Metalorganic Chemical Vapor Deposition (metalorganic chemical vapor deposition; MOCVD) under 1100 ℃, the thick n type GaN layer of growth one deck 2 μ m on the GaN resilient coating, wherein carrier concentration and mobility are respectively 6.7 * 10
17Cm
-3And 367cm
2/ V-S.
Then, on n type GaN layer, form electrode Ti/Al/Pt/Au of the present invention (25/100/50/200nm).In nitrogen (nitrogen) environment, respectively each sample is carried out annealing under different temperatures (750 ℃, 850 ℃ with 950 ℃) and the different time, and measure its feature contact resistance (specificcontact resistance; ρ C).The results are shown in Fig. 4.Example two
On sapphire substrate, at 520 ℃ of thick GaN resilient coatings of one deck 300nm of growing down.Then, the thick n type GaN layer of one deck 2 μ m because MOCVD under 1100 ℃, grows on the GaN resilient coating, wherein carrier concentration and mobility are respectively 6.7 * 10
17Cm
-3And 367cm
2/ V-S.Then, with the energy and 5 * 10 of 50KeV
15Cm
-2Dosage silicon is implanted in the n type GaN layer.
Then, on the n type GaN layer of implanted silicon, form electrode Ti/Al/Pt/Au of the present invention (25/100/50/200nm).In nitrogen environment, respectively each sample is carried out annealing under different temperatures (750 ℃, 850 ℃ with 950 ℃) and the different time, and measure its feature contact resistance (ρ C).The results are shown in Fig. 5.Example three
On sapphire substrate, in 520 ℃ of thick GaN resilient coatings of one deck 300nm of growing down.Then, the thick n type GaN layer of one deck 2 μ m because MOCVD under 1100 ℃, grows on the GaN resilient coating, wherein carrier concentration and mobility are respectively 6.7 * 10
17Cm
-3And 367cm
2/ V-S.Then, with the energy and 5 * 10 of 50KeV
15Cm
-2Dosage silicon is implanted in the n type GaN layer.Afterwards, in nitrogen environment, under 1050 ℃, annealed 30 minutes, recover (recovery), and simultaneously with the silicon activation of being implanted with the lattice that helps n type GaN layer.
Then, on the n type GaN layer of implanted silicon and recovery, form electrode Ti/Al/Pt/Au of the present invention (25/100/50/200nm).In nitrogen environment, respectively each sample is carried out annealing under different temperatures (750 ℃, 850 ℃ with 950 ℃) and the different time, and measure its feature contact resistance (ρ C).The results are shown in Fig. 6.Comparative example one
On sapphire substrate, at 520 ℃ of thick GaN resilient coatings of one deck 300nm of growing down.Then, the thick n type GaN layer of one deck 2 μ m because MOCVD under 1100 ℃, grows on the GaN resilient coating, wherein carrier concentration and mobility are respectively 6.7 * 10
17Cm
-3And 367cm
2/ V-S.
Then, on n type GaN layer, form the electrode Ti/Al/Au (25/100/200nm) of control group.In nitrogen environment, respectively each sample is carried out annealing under different temperatures (750 ℃, 850 ℃ with 950 ℃) and the different time, and measure its feature contact resistance (ρ C).The results are shown in Fig. 7.Comparative example two
On sapphire substrate, at 520 ℃ of thick GaN resilient coatings of one deck 300nm of growing down.Then, the thick n type GaN layer of one deck 2 μ m because MOCVD under 1100 ℃, grows on the GaN resilient coating, wherein carrier concentration and mobility are respectively 6.7 * 10
17Cm
-3And 367cm
2/ V-S.Then, with the energy and 5 * 10 of 50KeV
15Cm
-2Dosage silicon is implanted in the n type GaN layer.
Then, on the n type GaN layer of implanted silicon, form the electrode Ti/Al/Au (25/100/200nm) of control group.In nitrogen environment, respectively each sample is carried out annealing under different temperatures (750 ℃, 850 ℃ with 950 ℃) and the different time, and measure its feature contact resistance (ρ C).The results are shown in Fig. 8.Comparative example three
On sapphire substrate, at 520 ℃ of thick GaN resilient coatings of one deck 300nm of growing down.Then, the thick n type GaN layer of one deck 2um because MOCVD under 1100 ℃, grows on the GaN resilient coating, wherein carrier concentration and mobility are respectively 6.7 * 10
17Cm
-3And 367cm
2/ V-S.Then, with the energy and 5 * 10 of 50KeV
15Cm
-2Dosage silicon is implanted in the n type GaN layer.Afterwards, in nitrogen environment, under 1050 ℃, annealed 30 minutes, helping the recovery of n type GaN layer crystal lattice, and simultaneously with the silicon activation of being implanted.
Then, on the n type GaN layer of implanted silicon and recovery, form the electrode Ti/Al/Au (25/100/200nm) of control group.In nitrogen environment, respectively each sample is carried out annealing under different temperatures (750 ℃, 850 ℃ with 950 ℃) and the different time, and measure its feature contact resistance (ρ C).The results are shown in Fig. 9.
Data shown in the following table 1 can understand more that each example of the present invention creates conditions.
| Example one | Example two | Example three | Comparative example one | Comparative example two | Comparative example three |
Implanted silicon | | ??√ | ??√ | | ??√ | ??√ |
Recover (recover) | | | ??√ | | | ??√ |
???Ti/Al/Au | | | | ??√ | ??√ | ??√ |
???Ti/Al/Pt/Au | ??√ | ??√ | ??√ | | | |
The results are shown in | Fig. 4 | Fig. 5 | Fig. 6 | Fig. 7 | Fig. 8 | Fig. 9 |
Example one is that electrode Ti/Al/Pt/Au of the present invention contacts with n type GaN, and Fig. 4 is shown under the different annealing temperature its feature contact resistance for the functional arrangement of annealing time.In Fig. 4, minimum feature contact resistance ρ C appear at respectively 750 ℃ 8 * 10
-6Ω-cm
2: 850 ℃ 7 * 10
-6Ω-cm
2And 950 ℃ 7 * 10
-6Ω-cm
2Comparative example one is that electrode Ti/Al/Au contacts with n type GaN, and Fig. 7 is for showing that its feature contact resistance is for the functional arrangement of annealing time under the different annealing temperature.Comparison diagram 4 can find that with Fig. 7 the minimal characteristic contact resistance that Ti/Al/Pt/Au multilayer and Ti/Al/Au multilayer can produce when contacting with n type GaN is approximately equal.But the thermally-stabilised tolerance of Ti/Al/Pt/Au multilayer but is much better than the thermally-stabilised tolerance of Ti/Al/Au multilayer.
Example two is that electrode Ti/Al/Pt/Au contacts with the n type GaN of unrecovered implanted silicon, and Fig. 5 is shown under the different annealing temperature its feature contact resistance for the functional arrangement of annealing time.Comparative example two is that electrode Ti/Al/Au contacts with the n type GaN of unrecovered implanted silicon, and Fig. 8 is shown under the different annealing temperature its feature contact resistance for the functional arrangement of annealing time.As Fig. 5 and shown in Figure 8, under 750 ℃ annealing temperature, the feature contact resistance of two kinds of electrodes is similar for the relation of annealing time before 60 minutes.It should be noted that in comparative example two, obtain minimum feature contact resistance down can be the time at 60 minutes at 750 ℃, and after 60 minutes the feature contact resistance just along with the time increases considerably.But in example two, as shown in Figure 5, when annealing down for 750 ℃, along with the increase of annealing time, the feature contact resistance still little by little reduces.
In Fig. 5, minimum feature contact resistance ρ C appear at respectively 750 ℃ (more than 600 minutes) 7 * 10
-4Ω-cm
2850 ℃ (540 minutes) 7 * 10
-5Ω-cm
2And 950 ℃ (60 minutes) 2 * 10
-5Ω-cm
2According to Fig. 5 and experimental result shown in Figure 8, the thermal stability of electrode Ti/Al/Pt/Au of the present invention is much better than the electrode Ti/Al/Pt/Au of control group.The thermally-stabilised tolerance of ohm performance of Ti/Al/Pt/Au multilayer be respectively 850 ℃ 540 minutes with 950 ℃ 60 minutes, can be 750 ℃ of following annealing above 600 minutes.
To be electrode Ti/Al/Pt/Au contact with implanted silicon and the n type GaN that recovers example three, and Fig. 6 is shown under the different annealing temperature its feature contact resistance for the functional arrangement of annealing time.In Fig. 6, minimum feature contact resistance ρ C appears at about 3 * 10 under 750 ℃, 850 ℃ and 950 ℃ of the annealing temperatures
-6Ω-cm
2To be electrode Ti/Al/Au contact with implanted silicon and the n type GaN that recovers comparative example three, and Fig. 9 is shown under the different annealing temperature its feature contact resistance for the functional arrangement of annealing time.Comparison diagram 6 and the shown experimental result of Fig. 9, the electrode Ti/Al/Au of control group approximately equates with electrode Ti/Al/Pt/Au of the present invention getable minimal characteristic contact resistance under same annealing temperature.But the thermally-stabilised tolerance of electrode Ti/Al/Pt/Au of the present invention but is much better than the thermally-stabilised tolerance of Ti/Al/Au multilayer.
Once mentioned hereinbefore because the magnesium that is mixed in p type AlGaN layer 6 and the p type semiconductor layer 7 can form the Mg-H bond and the hole can't be provided, activated p type AlGaN layer 6 and p type semiconductor layer 7 to interrupt this Mg-H bond after forming p type semiconductor layer 7 so existing meeting is heat-treated.The condition that this heat treatment is used is generally at 700 to 750 ℃ and heated 15 to 60 minutes down.Yet, because the thermally-stabilised tolerance height of Ti/Al/Pt/Au multilayer of the present invention, so in its annealing manufacture craft, the effect that reaches activation p type AlGaN layer 6 and p type semiconductor layer 7 when forming ohmic contact is obviously without a doubt.Therefore, the manufacture craft of light-emitting diode of the present invention can be omitted existing activation step, and reaches same effect in follow-up manufacture craft.The manufacture craft of light-emitting diode of the present invention is described below with reference to Figure 10.
At first, shown in step 101, with resilient coating 2, n type semiconductor layer 3, n type AlGaN layer 4, active layers 5, p type AlGaN layer 6, be formed on substrate 1 top in regular turn with p type semiconductor layer 7.
Then, shown in step 102, with p type semiconductor layer 7, p type AlGaN layer 6, active layers 5, and n type AlGaN layer 4 partially-etched removing, so that the surface of n type semiconductor layer 3 is exposed.At this, the surperficial part of n type semiconductor layer 3 is also etched to be removed.
Then, shown in step 103, electrode 8A is formed on the n type semiconductor layer 3.Electrode 8A forms and can utilize existing deposition technique, for example vapour deposition method or sputtering method etc.In addition, by the explanation of above-mentioned each example as can be known, with electrode 8A be formed on the n type semiconductor layer 3 before, can the implanted silicon atom to this n type semiconductor layer and carry out the recovery of this n type semiconductor layer.
Afterwards, shown in step 104, the manufacture craft of annealing.The purpose of this step is for reducing the ohmic contact resistance of electrode 8A.This annealing manufacture craft is to carry out under 400 to 950 ℃ temperature.Simultaneously, under this heating condition, can reach the purpose of activation p type semiconductor layer 7.
Then, shown in step 105, electrode 8B is formed on the p type semiconductor layer 7, can be undertaken by for example vapour deposition method or sputtering method etc.After forming electrode 8B, can carry out the process annealing below 700 ℃, to reduce the ohmic contact resistance of electrode 8B.
As mentioned above, owing in step 104, can reach the effect of annealing and activation simultaneously,, thereby can reduce cost and increase production capacity so the manufacture method of compound semi-conductor device provided by the present invention can be than the simplification of existing manufacture craft.
The above, only in order to be used for convenient explanation preferred embodiment of the present invention, be not with narrow sense of the present invention be limited to this preferred embodiment.All according to any change that the present invention did, all belong to claim scope of the present invention.