CN101162751A - P type GaN cadmium-indium-oxygen transparent electrode and method for producing the same - Google Patents
P type GaN cadmium-indium-oxygen transparent electrode and method for producing the same Download PDFInfo
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- CN101162751A CN101162751A CNA2007100929126A CN200710092912A CN101162751A CN 101162751 A CN101162751 A CN 101162751A CN A2007100929126 A CNA2007100929126 A CN A2007100929126A CN 200710092912 A CN200710092912 A CN 200710092912A CN 101162751 A CN101162751 A CN 101162751A
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- conductive layer
- cadmium
- transparent electrode
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Abstract
The present invention discloses a cadmium indium oxygen (CIO) transparent electrode of P-type GaN; with the adoption of the CIO transparent conductive film structure, the light transmittance of the transparent electrode improves more 15 percent than that of the prior metal (Ni or Ni/Au) electrode; the invention can be applied to GaN-based blue-ray light-emitting diodes or laser diodes to improve luminous efficiency or can be applied to GaN-based photodetectors to improve responsivity, thereby having high industrial utility value. The invention also discloses a preparation method of transparent electrode which solves the problem that the COI transparent conductive film is difficult to achieve ohmic contact on the P-type GaN.
Description
Technical field
The present invention relates to ohmic contact scheme on a kind of P type GaN and preparation method thereof, relate in particular to a kind of P type GaN and go up cadmium-indium-oxygen transparent electrode and preparation method thereof.
Background technology
The GaN sill is the representative of third generation semiconductor material with wide forbidden band, has the performance of many excellences, in indigo plant, purple light emission, hyperfrequency, high temperature, many photoelectricity such as high-power and microwave device field wide application prospect is arranged.Along with commercialization and the practicability of high brightness basket, purple GaN base LED, the high brightness White LED might replace present various illuminating lamps, and lighting technology faces a new revolution.But present making for GaN base LED, also have some technical barriers not solve fully, wherein one of topmost difficult problem is: the P type carrier concentration that is difficult to obtain enough high concentrations in the material growth course, add that alternative metal material is limited, cause being difficult on GaN, making good P type Ohm contact electrode.Therefore, people find out the resistance that many methods reduce the last ohmic contact of P type GaN.Some researcher has just proposed employing gold and nickel material, and deposit Ni/Au successively on P type GaN anneals under the temperature more than 400 ℃ then, can obtain ohmic contact between metal and P type GaN.
On GaN base LED, adopt the Ni/Au metal to be: then to influence the even diffusion and the thermal stability of electric current when Ni/Au is too thin as the subject matter of P type GaN contact electrode; When too thick, the light transmittance of metallic film is low, greatly reduces the LED luminous efficiency.Therefore, the thickness of general employing Ni/Au is 50nm, and therefore light transmittance is lower than 50%., how to obtain the ohmic contact of low-resistance, high thermal stability and high transmission rate on P type GaN, thereby improve the LED luminous efficiency, be one of focal issue of numerous researchers' concerns always.For improving the luminous efficiency of LED, except the work of aspects such as encapsulating structure, optical design, one of method is to adopt nesa coating (TCO) to replace metal as the contact electrode on the P type GaN, to realize the even diffusion and the high transmission rate of electric current, exports thereby obtain higher light.
At present, most widely used transparent conductive film material is In
2O
3: Sn (ITO) and SnO
2: the F film.But ITO price height exists In easily to spread the problem that causes the device performance decay; SnO
2The problem that exist and be difficult to etching, generates the higher temperature (more than 400 ℃) of needs, simultaneously, these films all need could satisfy the needs of product by mixing, and can reduce the resistivity of film though mix, but also improved the absorption of charge carrier simultaneously, influenced the light transmittance of film light.Thereby people develop the ternary oxygenate that has higher light transmittance and lower resistivity under the situation that need not painstakingly to mix, for example CdIn
2O
4(CIO), Cd
2SnO
4, MgIn
2O
4, MgAl
2O
4And SnZn
2O
4And corresponding mixture, this is the broad-band gap oxide film material that a class has spinel structure, owing to can come gradual change ground to regulate its photoelectric properties by the ratio of regulating between the constituent element, thereby obtained extensive concern in the transparent conductive film field.
With SnO
2, transparent conductive film material such as ITO compares, CIO has the following advantages:
(1) low-down resistivity (10
-4The Ω .cm order of magnitude) and high transmission rate (visible region light transmittance greater than 90%, the reflectivity of infrared light region up to 93%).
(2) just can reach very low resistivity without any need for mixing.Maximum ITO need mix tin, SnO for present commercial application
2Need mix F etc. and just can reach good effect, and the CIO film just can reach excellent photoelectric performance without any need for painstakingly doping, and its photoelectric properties can easily realize regulating by the ratio of adjusting Cd and In.
(3) it is more cheap to compare the ito thin film price.Because CIO is a ternary compound, the price of Cd is more cheap than In, so average price is more cheap than ito thin film.
(4) shortwave is corresponding good.Compare SnO
2Chemical property more stable, higher resistance to wear and strong resistance to chemical corrosion.
But directly with CdIn
2O
4Thin film deposition is difficult to obtain ohmic contact after the Alloying Treatment on P type GaN, reason is: (1) P type GaN energy gap is 3.4eV, and electron affinity energy is 4.1eV, and work function very big (7.5eV) is with CdIn
2O
4The barrier height that contact forms is big; (2) P type GaN is difficult to realize heavy doping, and Mg doping content in P type GaN is 10 usually
20Cm
-3, but because Mg can form the deep acceptor energy level in P type GaN, and its ionization energy very high (～170meV), according to Fermi-Dirac statistics, the ionization level of Mg dopant approximately is 1%, causes carrier concentration to be difficult to surpass 10
18Cm
-3In addition, Mg also can form complex compound Mg-H (being the hydrogen passivation) with the hydrogen in the material, and the remaining acceptor impurity of compensated part, and the hole concentration of P type GaN is further reduced, and has limited forming the required tunnel current of low resistance ohmic contact; (3) be easy in the technical process reduce the hole concentration on P type GaN surface in the N room of P type GaN surface generation as the alms giver.In addition, the condition of metallization process also can influence P type GaN contact resistivity.Therefore, on P type GaN, form ohmic contact, need reduce barrier height, thus consider that inserting intermediate metal layer between with transparent oxide film and Semiconductor substrate reduces barrier height, thus reduction specific contact resistivity rate.
Summary of the invention
The object of the present invention is to provide and a kind ofly on P type GaN, realize ohmic contact scheme of low-resistance, high transmission rate and preparation method thereof.
A kind of P type GaN goes up cadmium-indium-oxygen transparent electrode, and it comprises: a P type GaN, on P type GaN, first conductive layer is arranged, and CIO (cadmium indium oxygen) transparent conductive film is arranged on first conductive layer; Can between described first conductive layer and CIO transparent conductive film, deposit second conductive layer again.
The metal material that described first conductive layer adopts can be: a kind of among Ni, Pt, Pd, Ru, Re, the Cu; Described second conductive layer, the metal material that is adopted can be a kind of among Au, Cr, the Ir.
The thickness range of described first conductive layer can be 2 to 100 dusts, and the thickness range of described second conductive layer can be 2 to 100 dusts; The thickness range of described CIO transparent conductive film (3) can be 100 to 1000nm.
P type GaN goes up the preparation method of cadmium-indium-oxygen transparent electrode, and its processing step is:
1) on P type GaN in the physical vapour deposition (PVD) mode, deposit first conductive layer;
2) on first conductive layer in the physical vapour deposition (PVD) mode, deposition CIO transparent conductive film;
3) carry out alloying heat treatment.
After step 1), can also deposit second conductive layer that a thermally-stabilised metallic film is constituted again.
The deposition process of first conductive layer and second conductive layer can be electron beam evaporation plating, hot evaporation or sputter.
The deposition process of the CIO transparent conductive film step 2) can be sputter or electron beam evaporation plating.
Aforesaid preparation method's concrete steps are:
Step 1) immerses 3-5min in the wang aqueous solution with P type GaN, and employing acetone, alcohol and deionized water difference sonic oscillation 5min, sample is dried up with nitrogen, place the electron gun deposition system immediately, vacuumizing, is the metal Ni of 5nm at P type GaN hydatogenesis thickness, and its process conditions are: high pressure 6KV, line 155mA, operating air pressure: 2.2 * 10
-3Pa;
Step 2) adopt direct current magnetron sputtering process on P type GaN/Ni, to deposit the CdIn of 200nm
2O
4It is that 99.99% diameter is the Cd-In alloy target material of 6cm that film, target raw material are selected purity for use, and the atomic ratio of Cd, In is 1: 2, and its technological parameter is: operating pressure: 3.1Pa, oxygen concentration 4.29%, sputtering power 50W, 250 ℃ of substrate temperatures, target-substrate distance 7.5cm;
Alloying heat treatment described in the step 3) is in oxygen or air, annealing in process 1-5min in 400 ℃ of-700 ℃ of scopes.
Useful technique effect of the present invention is: the light transmittance of CIO transparency electrode improves more than 15% than traditional metal (Ni or Ni/Au) electrode, be expected to be applied to GaN base blue LED or laser diode and improve its light extraction efficiency, or be applied to improve its responsiveness on the GaN base photodetector, have high industrial utilization; The invention also discloses the preparation method of above-mentioned transparency electrode, this method has solved the CIO transparent conductive film is difficult to obtain ohmic contact on P type GaN problem.
Description of drawings
Accompanying drawing 1, P type GaN goes up the cadmium-indium-oxygen transparent electrode structural representation;
Accompanying drawing 2, the structural representation when on first conductive layer, depositing second conductive layer again;
Accompanying drawing 3, the X-ray diffractogram of CIO transparent conductive film;
Accompanying drawing 4, the light transmittance curve of Ni/CIO film and Ni film;
Accompanying drawing 5, the I-V curve under the different annealing temperature in the air behind the last deposition of the P type GaN Ni/CIO film.
In the accompanying drawing: P type GaN 1, the first conductive layer 2, CIO transparent conductive film 3, the second conductive layers 4.
Embodiment
Embodiment 1: referring to accompanying drawing 1, one P type GaN 1, first conductive layer 2 is arranged on P type GaN 1, it is characterized in that: on first conductive layer 2, CIO transparent conductive film 3 is arranged, and the situation when this example includes only first conductive layer 2 for conductive layer, its step is as follows:
1) with P type GaN 1 (carrier concentration 3.37 * 10
17Cm
-3, mobility 4.34cm
2/ V.s) immerse 3-5min in the wang aqueous solution, and adopt acetone, alcohol and deionized water sonic oscillation 5min (purpose is in order to remove surface impurity and oxide layer, to reduce barrier height) respectively;
2) sample that obtains in the previous step is dried up with nitrogen, place the electron gun deposition system immediately, vacuumize, at P type GaN 1 hydatogenesis thickness is the metal Ni (i.e. first conductive layer 2) of 5nm, its process conditions are: high pressure 6KV, line 155mA, operating air pressure: 2.2 * 10
-3Pa;
3) adopt direct current magnetron sputtering process on P type GaN/Ni, to deposit the CdIn of 200nm
2O
4It is that 99.99% diameter is the Cd-In alloy target material of 6cm that film (being CIO transparent conductive film 3), target raw material are selected purity for use, and the atomic ratio of Cd, In is 1: 2, its technological parameter is: operating pressure: 3.1Pa, oxygen concentration 4.29%, sputtering power 50W, 250 ℃ of substrate temperatures, target-substrate distance 7.5cm;
4) in air, in 400 ℃ of-550 ℃ of scopes sample is carried out alloying annealing in process 1min.
Referring to accompanying drawing 3, the X-ray diffractogram of the CIO transparent conductive film 3 that obtains in the present embodiment, visible CIO nesa coating 3 is polycrystalline structures, it comprises a large amount of CIO phase and a spot of In
2O
3Reach the CdO phase of trace mutually.
The main performance of the CIO transparent conductive film 3 for preparing under present embodiment step 3) process conditions is: resistivity is 2.95 * 10
-4Ω .cm; Carrier concentration is 3.508 * 10
20Cm
-3The charge carrier hall mobility is 60.32cm
2/ V.S, in the visible region, the light transmittance of film was up to 91.7% when wavelength was 628nm.
Referring to accompanying drawing 4, the comparison diagram of Ni/CIO film that obtains and Ni film light transmittance, as seen, in the 400-600nm wave-length coverage, when Ni thickness is 5nm, light transmittance is about 50%, when the Ni film thickness is 10nm, light transmittance only is about 20%, and annealing back Ni (5nm)/CIO (200nm) and Ni (10nm)/CIO (200nm) film light transmittance are respectively about 65% and about 55%, promptly compare with the Ni metal film of respective thickness, Ni (5nm)/CIO (200nm) and Ni (10nm)/CIO (200nm), the Ni/CIO light transmittance improves respectively about 15% and 30%, illustrates to adopt CIO as transparent electrode material, can obviously improve the light transmittance of electrode.
Referring to accompanying drawing 5, after inserting layer of metal Ni (5nm) between P type GaN 1 and the CIO transparent conductive film 3, to unannealed sample and the I-V curve of the sample of annealing behind the 1min in 400 ℃, 500 ℃, 550 ℃ air respectively, as seen: unannealed sample I-V is a curve, present rectification characteristic, cut-in voltage is bigger; 400 ℃ is straight line with 500 ℃ of sample I-V curves of annealing down down, shows that sample after annealing under 400 ℃ and 500 ℃, is ohmic contact characteristic, and the specific contact resistivity rate is distributed as 3.2 * 10
-4Ω .cm
2With 4.9 * 10
-4Ω .cm
2When annealing temperature was elevated to 550 ℃, curve ratio was more curved, showed that contact begins to present rectification characteristic again.
Embodiment 2: referring to accompanying drawing 1, accompanying drawing 2, this example is for depositing the situation of one second conductive layer 4 again between first conductive layer 2 and CIO transparent conductive film 3, and its step is as follows:
1) P type GaN 1 is immersed 3-5min in the wang aqueous solution, and adopt acetone, alcohol and deionized water sonic oscillation 5min (purpose is in order to remove surface impurity and oxide layer, to reduce barrier height) respectively;
2) sample that previous step is obtained dries up with nitrogen, place the electron gun deposition system immediately, vacuumize, at P type GaN 1 hydatogenesis thickness is the metal Ni (i.e. first conductive layer 2) of 5nm, then adopt with quadrat method at the thick golden Au (i.e. second conductive layer 4) of deposition one deck 5nm, its process conditions are: high pressure 6KV, line 155mA, operating air pressure: 2.2 * 10
-3Pa);
3) use direct current magnetron sputtering process on P type GaN/Ni/Au, to deposit the CdIn of 200nm
2O
4It is that 99.99% diameter is the Cd-In alloy target material of 6em that film (being CIO transparent conductive film 3), target raw material are selected purity for use, and the atomic ratio of Cd, In is 1: 2, its technological parameter is: operating pressure: 3.1Pa, oxygen concentration 4.29%, sputtering power 50W, 250 ℃ of substrate temperatures, target-substrate distance 7.5cm;
4) resulting sample in air, 500 ℃ of following alloying annealing in process 1min.
Claims (10)
1. a P type GaN goes up cadmium-indium-oxygen transparent electrode, and it comprises: a P type GaN (1), first conductive layer (2) is arranged on P type GaN (1), and it is characterized in that: CIO transparent conductive film (3) is arranged on first conductive layer (2).
2. P type GaN according to claim 1 goes up cadmium-indium-oxygen transparent electrode, it is characterized in that: can deposit one second conductive layer (4) again between described first conductive layer (2) and CIO transparent conductive film (3).
3. P type GaN according to claim 2 goes up cadmium-indium-oxygen transparent electrode, it is characterized in that: the metal material that described first conductive layer (2) adopts can be: a kind of among Ni, Pt, Pd, Ru, Re, the Cu; Described second conductive layer (4), the metal material that is adopted can be a kind of among Au, Cr, the Ir.
4. go up cadmium-indium-oxygen transparent electrode according to claim 2 or 3 described P type GaN, it is characterized in that: the thickness range of described first conductive layer (2) can be 2 to 100 dusts, and the thickness range of described second conductive layer (4) can be 2 to 100 dusts.
5. P type GaN according to claim 1 goes up cadmium-indium-oxygen transparent electrode, it is characterized in that: the thickness range of described CIO transparent conductive film (3) can be 100 to 1000nm.
6. a P type GaN goes up the preparation method of cadmium-indium-oxygen transparent electrode, and it is characterized in that: its processing step is:
1) goes up in the physical vapour deposition (PVD) mode at P type GaN (1), deposit first conductive layer (2);
2) go up in the physical vapour deposition (PVD) mode deposition CIO transparent conductive film (3) at first conductive layer (2);
3) carry out alloying heat treatment.
7. P type GaN according to claim 6 goes up the preparation method of cadmium-indium-oxygen transparent electrode, it is characterized in that: after step 1), can also deposit second conductive layer (4) that a thermally-stabilised metallic film is constituted again.
8. P type GaN according to claim 7 goes up the preparation method of cadmium-indium-oxygen transparent electrode, and it is characterized in that: the deposition process of first conductive layer (2) and second conductive layer (4) can be electron beam evaporation plating, hot evaporation or sputter.
9. P type GaN according to claim 8 goes up the preparation method of cadmium-indium-oxygen transparent electrode, it is characterized in that: step 2) described in the deposition process of CIO transparent conductive film (3) can be sputter or electron beam evaporation plating.
10. P type GaN according to claim 6 goes up the preparation method of cadmium-indium-oxygen transparent electrode, it is characterized in that:
The described deposition process of step 1) is: P type GaN (1) is immersed 3-5min in the wang aqueous solution, and employing acetone, alcohol and deionized water difference sonic oscillation 5min, sample is dried up with nitrogen, place the electron gun deposition system immediately, vacuumizing, is the metal Ni of 5nm at P type GaN (1) hydatogenesis thickness, and its process conditions are: high pressure 6KV, line 155mA, operating air pressure: 2.2 * 10
-3Pa;
Step 2) described deposition process is: adopt direct current magnetron sputtering process to deposit the CdIn of 200nm on P type GaN/Ni
2O
4It is that 99.99% diameter is the Cd-In alloy target material of 6cm that film, target raw material are selected purity for use, and the atomic ratio of Cd, In is 1: 2, and its technological parameter is: operating pressure: 3.1Pa, oxygen concentration 4.29%, sputtering power 50W, 250 ℃ of substrate temperatures, target-substrate distance 7.5cm;
The described alloying heat treatment of step 3) is in oxygen or air, annealing in process 1-5min in 400 ℃ of-700 ℃ of scopes.
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|---|---|---|---|
| CNB2007100929126A CN100505350C (en) | 2007-10-30 | 2007-10-30 | P type GaN cadmium-indium-oxygen transparent electrode and method for producing the same |
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| CN100505350C CN100505350C (en) | 2009-06-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103107244A (en) * | 2013-02-17 | 2013-05-15 | 淮阴师范学院 | Preparation method for electroconductive film with cadmium oxide base light-transmitting waveband adjustable |
| CN104835716A (en) * | 2015-03-18 | 2015-08-12 | 浙江大学 | Transparent conductive oxide film based on Ir interlayer doping |
| CN105720142A (en) * | 2016-03-23 | 2016-06-29 | 华灿光电股份有限公司 | Fabrication method of light emitting diode chip |
| CN107316877A (en) * | 2016-04-19 | 2017-11-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | X-ray detector and preparation method thereof |
-
2007
- 2007-10-30 CN CNB2007100929126A patent/CN100505350C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103107244A (en) * | 2013-02-17 | 2013-05-15 | 淮阴师范学院 | Preparation method for electroconductive film with cadmium oxide base light-transmitting waveband adjustable |
| CN103107244B (en) * | 2013-02-17 | 2015-12-02 | 淮阴师范学院 | The conductive film preparation method that a kind of cadmium oxide base transmission region is adjustable |
| CN104835716A (en) * | 2015-03-18 | 2015-08-12 | 浙江大学 | Transparent conductive oxide film based on Ir interlayer doping |
| CN105720142A (en) * | 2016-03-23 | 2016-06-29 | 华灿光电股份有限公司 | Fabrication method of light emitting diode chip |
| CN105720142B (en) * | 2016-03-23 | 2018-10-09 | 华灿光电股份有限公司 | A kind of preparation method of light-emitting diode chip for backlight unit |
| CN107316877A (en) * | 2016-04-19 | 2017-11-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | X-ray detector and preparation method thereof |
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