CN1136608C - Activation method for reducing P type doping film resistance by plasma - Google Patents
Activation method for reducing P type doping film resistance by plasma Download PDFInfo
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- CN1136608C CN1136608C CNB011090308A CN01109030A CN1136608C CN 1136608 C CN1136608 C CN 1136608C CN B011090308 A CNB011090308 A CN B011090308A CN 01109030 A CN01109030 A CN 01109030A CN 1136608 C CN1136608 C CN 1136608C
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Abstract
The present invention relates to a method for activating a high resistance P type thin membrane into a low resistance P type thin membrane, wherein the high resistance P type thin membrane is a P type doped metal nitride thin membrane of group three or a P type doped compound thin membrane of group two to six. The characteristic that active gas is easy to combine with hydrogen atoms is used, and a radio-frequency generator or an electron beam is used for converting the active gas into plasma. At the time of heat annealing, the plasma assists the P type doped atoms to separate with the hydrogen atoms so as to achieve the purpose of activating the P type doped thin membrane. Thus, temperature and time for heat annealing treatment can be reduced, and diffusion problems brought by high temperature and long time heat treatment can be reduced. The reliability of elements is enhanced, and the purpose of rapid production is achieved simultaneously.
Description
Technical field
The present invention relates to reduce the activation method of P type doping film resistance, particularly relate to the activation method that uses plasma (plasma) to reduce P type doping film resistance.
Background technology
Because the III family metal nitride (III-Nitride) of wide energy gap (wide band gap), as gallium nitride (GaN), InGaN (InGaN), aluminium gallium nitride alloy (AlGaN), aluminum indium gallium nitride (AlGaInN) etc., and two-six compounds of group of wide energy gap (II-VI compound semiconductor), as ZnSe, ZnMgSe etc., has good photoelectric characteristic, be made into film morphology widely in recent years and on photoelectric cell, used, as light-emitting diode (LEDs) and laser diode (LDs).But, when above-mentioned material is made into film morphology, on using, still has certain difficulty and restriction, thereby hindered the development of opto-electronics.
With the gallium nitride is example, owing to lack suitable substrate, so up to the present in the making of gallium nitride film, still the aluminium oxide (sapphire) that uses lattice not to be complementary, by technology, cooperate organic metal vapor deposition (Metal-Organic Chemical Vapor Deposition by the resilient coating of growing up on the aluminum oxide substrate (buffer layer); Be designated hereinafter simply as mocvd method) the manufacturing gallium nitride film.Gallium nitride film is mixing p type impurity, and during as beryllium (Be), magnesium (Mg), calcium (Ca), zinc (Zn), cadmium elements such as (Cd), p type impurity is very easy to and the hydrogen in the reacting gas combines, thereby the P type gallium nitride film that causes forming presents the state of high value.According to the P type gallium nitride film that conventional method forms, its film resistance generally is higher than 10
5Ω-cm, and its hole concentration generally is lower than 10
12Cm
-3, therefore on using, be severely limited.
The I.Akasaki of Japan Nagoya university and H.Amano use low energy electrons bundle irradiation (Low Energy Electron Beam Irradiation; LEEBI) handle the gallium nitride film that is doped with Mg, its activation is obtained P type gallium nitride film.But the method that Nagoya University proposes is because activating velocity is too slow, and near the film can only activating surface, so and impracticable.
The S.Nakamura of Ri Ya chemical company uses two air-flow Metalorganic chemical vapor deposition methods and low temperature gallium nitride resilient coating to come the gallium nitride growth film.Utilize the mode of conventional high-temperature annealing (annealing) again, P type (doped with Mg) gallium nitride film of high value is activated into the P type gallium nitride film of low resistance.The condition of annealing is under the nitrogen environment, and temperature continues more than one minute between 400 ℃ to 1200 ℃.If add the time of intensification, cooling, whole annealing process can be more than 10 minutes.Because annealing (heat treatment) overlong time, therefore when on the contact-making surface of different medium or light-emitting diode, using, long-time high-temperature activation P type gallium nitride film, each composition of layer is changed or make the doping on composition surface (junction) produce diffusion, and may and then influence its photoelectric characteristic because of diffusion problem.
Summary of the invention
At above-mentioned situation, the present inventor is through concentrated research, discovery utilizes active gases and the outstanding binding ability of hydrogen, make above-mentioned active gases form long-distance plasma (remote plasma) with radio frequency (RF) maker, p type impurity in the film is interrupted with combining of hydrogen, hydrogen atom is shifted from P type doping film, thereby the P type doping film of high value is activated into the P type doping film of low resistance, finish the present invention.
The object of the present invention is to provide a kind of activation method of the P of reduction type doping film resistance, specifically, the object of the present invention is to provide a kind of use plasma (plasma) to reduce the activation method of P type doping film resistance.
The present invention proposes utilizes plasma (plasma) that activating high-resistance P type doping film is become the method for low-resistance P type doping film, comprises the steps:
The one P type doping film is provided, for example obtains by the mocvd method manufacturing;
On an above-mentioned P type doping film, plate layer protective layer earlier, for example oxide (silicon dioxide), nitride (silicon nitride) or metal etc.;
To feed around the P type doping film easily and hydrogen carries out reactive activity gas (for example oxygen, N again
2O) long-distance plasma, or the plasma of the mist of inert gas and above-mentioned active gases (plasma).Above-mentioned long-distance plasma is produced by radio frequency (RF) maker, direct current (DC) maker, microwave maker or electron cyclotron resonace (ECR);
Heat an above-mentioned P type doping film, make temperature rise to first specified temp (this first specified temp 100 ℃ to 1200 ℃ scope) by initial temperature, temperature time that this first specified temp is kept more than or equal to 0 second;
Cool the temperature to initial temperature again; And
Remove protective layer at last.
Wherein, the material of above-mentioned P type high value film is an III family metal nitride (III-Nitride), and (chemical general formula is: Al as gallium nitride (GaN), InGaN (InGaN), aluminium gallium nitride alloy (AlGaN), aluminum indium gallium nitride (AlGaInN) etc.
xGa
yIn
1-x-yN, wherein 0≤X≤1,0≤Y≤1 and x+y≤1), or two-six compounds of group, as ZnSe, ZnMgS etc.
By said method the one P type doping film is activated into the 2nd P type doping film, and the resistance of above-mentioned the 2nd P type doping film is lower than the resistance of an above-mentioned P type gallium nitride film.
The present invention uses the activation method of plasma (plasma) reduction P type doping film resistance, and is all suitable for the face that connects of individual layer, Bulk P type gallium nitride (bulk P-type GaN) and same media or different medium.Describe the present invention below in detail, and advantage of the present invention is described by embodiment.
Embodiment
The present invention uses plasma (plasma) to reduce the activation method of P type doping film resistance, comprises the steps:
At first, provide a P type doping film, can use Metalorganic chemical vapor deposition method (MOCVD) manufacturing to obtain.Owing to mix the p type impurity of film, as beryllium (Be), magnesium (Mg), calcium (Ca), barium (Ba), cadmium (Cd) or zinc elements such as (Zn), hydrogen very easy and in the reacting gas combines, can't manifest the due characteristic of p type impurity, so cause an above-mentioned P type doping film can present the high value state inevitably.
An above-mentioned P type doping film also can be grown up by molecular beam epitaxy (molecular beamepitaxy (MBE method) growth) or halide chemical vapour deposition technique (HVPE) manufacturing obtains.
On a P type doping film, plate layer protective layer, as silicon dioxide (SiO
2), silicon nitride (Si
3N
4) or metal (for example nickel (Ni)) etc., thereby protect above-mentioned P type doping film surface can not destroyed by the long-distance plasma that later step feeds, reduce membrane quality.
Feed around the P type doping film easily and hydrogen carries out reactive activity gas.Above-mentioned active gases such as oxygen (O
2), nitrogen oxide (NO), nitrous oxide (N
2O) etc., the perhaps mist that forms by above-mentioned active gases and inert gas, but in above-mentioned mist, it is more than 5% that above-mentioned active gases accounts for whole ratio.In addition, long-distance plasma is ordered about above-mentioned active gases or mist generation by radio frequency (RF) maker, direct current (DC) maker, microwave maker or electron cyclotron resonace (ECR).
Heat an above-mentioned P type doping film, temperature is heated to the first specified temp T by initial temperature, this temperature can be from 100 ℃ to 1200 ℃ scope, and then the thermal annealing temperature rests on first specified temp and reaches certain hour t.According to the needs of practical application, the length of this certain hour t can be more than or equal to 0 second, and then cools the temperature to initial temperature.Wherein, during above-mentioned time t=0, expression when being heated to first specified temp, the operation of lowering the temperature immediately.In addition, the heating operation to an above-mentioned P type doping film can use boiler tube, the annealing system that is rapidly heated (RTA) and radio frequency (RF) maker carry out.
The scope of above-mentioned first specified temp is 100 ℃ to 1200 ℃, all can reach activating high-resistance P type doping film in this scope, and reduce the purpose of its resistance.But, when above-mentioned first specified temp surpasses 1000 ℃, owing to a P type gallium nitride film might react with the reactive gas plasma (plasma) of auxiliary usefulness, so can reduce the quality of P type doping film a little.Therefore first specified temp among the present invention is preferred 100 ℃～1000 ℃, to obtain best activation quality.
At last, remove protective layer, promptly finish the present invention, a P type doping film is activated into the 2nd P type doping film of low resistance.
Cardinal principle of the present invention is a characteristic of utilizing active gases easily to combine with hydrogen atom, assist to destroy combining between hydrogen atom and the p type impurity (for example Mg) with the plasma (plasma) of above-mentioned gas, thus the required temperature and time of reduction P type doping film activation process.In the method, though still a P type doping film must be heated to the first specified temp T, to promote the carrying out of reaction, temperature required low than existing thermal annealing temperature.With P type gallium nitride film is example, according to method of the present invention, can obtain hole concentration greater than 10
17Cm
-3, film resistance is less than 10 Ω-cm.Yet the present invention is not limited to activate P type gallium nitride film, every III family's metal nitride (III-Nitride), and (chemical general formula is: Al as InGaN (InGaN), aluminium gallium nitride alloy (AlGaN), aluminum indium gallium nitride (AlGaInN) etc.
xGa
yIn
1-x-yN, wherein 0≤X≤1,0≤Y≤l and x+y≤1), or two-six compounds of group, as ZnSe, ZnMgSe etc., formed P type doping film all can be used method of the present invention to reduce resistance.
At present, the most frequently used the high-resistance P type gallium nitride film being activated into the method for low-resistance P type gallium nitride film, is the method that adopts aforementioned Ri Ya chemical company to propose.But in the method for Ri Ya chemical company, carrying out the condition of thermal annealing, must be under the environment that is full of nitrogen or other inert gases, and design temperature (is set at 700 ℃) usually between 400 ℃ to 1200 ℃, and keeps more than one minute.As mentioned above, if add the time of intensification, cooling, whole annealing process is more than 10 minutes, so P type gallium nitride film may produce the problem of diffusion at different layers because of long-time high-temperature heat treatment, and then influences its function, effect.
But, adopt method of the present invention, can hold the temperature time with low temperature or short thermal annealing and reach the purpose of activation, so promptly be used in the face that connects or the light-emitting diode of different medium, to the variation of each composition of layer of P type gallium nitride film or connect the mix problem of diffusion of face (junction), all can reduce because of the reduction of heat treatment temperature or the shortening of heat treatment time.
The foregoing description is preferred embodiment of the present invention, but can not be used for limiting the present invention, the variation that those of ordinary skills are made according to the present invention and revise and all should be included in protection scope of the present invention.
Claims (9)
1, a kind of activation method that uses plasma to reduce P type doping film resistance comprises:
The one P type doping film is provided, and wherein, a P type doping film is III family metal nitride film or two-six compound semiconductor films;
On an above-mentioned P type doping film, form protective layer;
Use long-distance plasma that an above-mentioned P type doping film is handled, wherein, this long-distance plasma contains easily and first active gases of hydrogen reaction;
Heat an above-mentioned P type doping film, make temperature rise to 100 ℃～1200 ℃ first specified temp, and keep time more than or equal to 0 second at this first specified temp by initial temperature;
Temperature is reduced to initial temperature by above-mentioned first specified temp;
Remove above-mentioned protective layer,
Wherein, an above-mentioned P type doping film is activated into the 2nd P type film, and the resistance of above-mentioned the 2nd P type film is lower than an above-mentioned P type film.
2, use plasma as claimed in claim 1 reduces the activation method of P type doping film resistance, and described protective layer is selected from one of oxide, nitride or metal.
3, use plasma as claimed in claim 1 reduces the activation method of P type doping film resistance, and described first active gases is selected from one of mist of oxygen, nitrogen oxide, nitrous oxide or they and inert gas formation.
4, use plasma as claimed in claim 3 reduces the activation method of P type doping film resistance, and the ratio of first active gases is greater than 5% in the described mist.
5, use plasma as claimed in claim 1 reduces the activation method of P type doping film resistance, and described long-distance plasma is produced by radio-frequency generator, direct current maker, microwave maker or electron cyclotron resonace.
6, use plasma as claimed in claim 1 reduces the activation method of P type doping film resistance, and described heating operation uses boiler tube, be rapidly heated annealing system or radio-frequency generator carry out.
7, use plasma as claimed in claim 1 reduces the activation method of P type doping film resistance, and described P type doping film uses Metalorganic chemical vapor deposition method, molecular beam epitaxy to grow up or the halide chemical vapour deposition technique is made.
8, use plasma as claimed in claim 1 reduces the activation method of P type doping film resistance, and the material of described P type doped with II I family metal nitride film is selected from Al
xGa
yIn
1-x-yN, wherein 0≤X≤1,0≤Y≤1 and x+y≤1.
9, use plasma as claimed in claim 1 reduces the activation method of P type doping film resistance, and in the film of described P type doped with II I family metal nitride, p type impurity is selected from beryllium, magnesium, calcium, barium, cadmium or zinc.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011090308A CN1136608C (en) | 2001-02-27 | 2001-02-27 | Activation method for reducing P type doping film resistance by plasma |
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|---|---|---|---|
| CNB011090308A CN1136608C (en) | 2001-02-27 | 2001-02-27 | Activation method for reducing P type doping film resistance by plasma |
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| CN1136608C true CN1136608C (en) | 2004-01-28 |
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| CN108538714B (en) * | 2018-04-19 | 2021-06-15 | 中国电子科技集团公司第十三研究所 | preparation method of p-type III-group nitride material |
| CN108447788B (en) * | 2018-04-19 | 2021-10-15 | 中国电子科技集团公司第十三研究所 | Preparation method of enhanced high electron mobility transistor |
| CN112331745B (en) * | 2020-10-27 | 2022-04-12 | 华灿光电(苏州）有限公司 | Preparation method of light emitting diode epitaxial wafer |
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