CN1158697C - Method for activating hihg-resistance P type film into low-resistance P type film - Google Patents
Method for activating hihg-resistance P type film into low-resistance P type film Download PDFInfo
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- CN1158697C CN1158697C CNB011090324A CN01109032A CN1158697C CN 1158697 C CN1158697 C CN 1158697C CN B011090324 A CNB011090324 A CN B011090324A CN 01109032 A CN01109032 A CN 01109032A CN 1158697 C CN1158697 C CN 1158697C
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Abstract
The present invention relates to a fabrication method for activating a high resistance P type thin membrane into a low resistance P type thin membrane. Energy which is generated by temperature gradient change is used for activating a high resistance P type doped thin membrane into a low resistance P type doped thin membrane. The high resistance P type thin membrane is a P type doped metal nitride thin membrane of a group III or is a P type doped compound thin membrane of groups II to VI. In a temperature gradient change process, time for temperature holding operation is shorter than 1 minute. A rapid temperature raising method is used for achieving P type doping and shortening the time of heat treatment. Thus, diffusion problems derived by long time heat treatment is reduced.
Description
Technical field
The present invention is the manufacture method that the high-resistance P type film is activated into the low-resistance P type film, particularly relevant for utilizing fast temperature to change, the film of high-resistance P type doping is activated into the activation method of the low resistance film of P type doping.
Background technology
Because the III family metal nitride (III-Nitride) of wide energy gap is as gallium nitride (GaN), InGaN (InGaN), aluminium gallium nitride alloy (AlGaN), aluminum indium gallium nitride (AlGaInN) ... etc.; And the II-VI compounds of group of wide energy gap is as P-ZnSe, ZnMgSe... etc., has superior photoelectric characteristic, so above-mentioned material also was made into film shape in recent years widely, to be applied on the photoelectric cell, for example: light-emitting diode (LEDs) and laser diode (LDs).Yet, when above-mentioned material is made filminess, on using, it still has some difficulties and restriction, hindered the progress 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 uses the unmatched aluminium oxide of lattice (sapphire); Mainly, cooperate organic metal vapor deposition (Metal Organic ChemicalVapor Deposition again by the technology of the resilient coating of growing up on the aluminum oxide substrate (buffer layer); Be designated hereinafter simply as mocvd method) to form gallium nitride film.Gallium nitride film is mixing p type impurity, as: during elements such as beryllium Be, magnesium Mg, calcium Ca, zinc Zn, cadmium Cd, above-mentioned p type impurity hydrogen very easy and in the reacting gas combines, and causes formed P type gallium nitride film can present the high value state.According to the P type gallium nitride film that traditional approach forms, its film resistance often is higher than 10
5Ω cm, and its hole concentration often is lower than 10
12Ω cm
-3, also therefore on using, be severely limited.
The I.Akasaki of Japan Nagoya university and H.Amano use low energy electrons bundle (LEEBI; LowEnergy Electron Beam Irradiation) treatment with irradiation is doped with the gallium nitride film of Mg, and its activation is obtained P type gallium nitride film.Its major defect is: the method that Nagoya University proposed, because active rate is too slow, and have only near the film the activating surface, so and impracticable.
The S.Nakamura of Ri Ya chemical company then 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.Its major defect is: the condition of carrying out of its annealing is under the environment of nitrogen, between temperature 400-1200 ℃, is holding temperature on the specified temp more than 1 minute; Add the time of heating up and lowering the temperature, the process of whole annealing can surpass more than 10 minutes.Because the time of annealing (heat treatment) is long, therefore in the time of on being applied in heterojunction or light-emitting diode, the high temperature of P type gallium nitride film activates for a long time, each composition of layer is formed to change, or make the doping on composition surface (junction) produce diffusion, and may be, and then influence its photoelectric characteristic because of the diffusion problem that long heat treatment produced.
Summary of the invention
The object of the present invention is to provide a kind of the high-resistance P type film to be activated into the manufacture method of low-resistance P type film, utilize temperature gradient to change the energy drives power that is produced, the film of high-resistance P type doping is activated into the film of low-resistance P type doping; Wherein, the material of above-mentioned P type high value film is: III family metal nitride (III-Nitride), as gallium nitride (GaN), InGaN (InGaN), aluminium gallium nitride alloy (AlGaN), aluminum indium gallium nitride (AlGaInN) ... etc.; And the II-VI compounds of group is as ZnSe, ZnMgSe... etc.
The object of the present invention is achieved like this: the film of high-resistance P type doping is activated into the manufacture method of the film of low-resistance P type doping, comprise the steps:
The film that provides a P type to mix is for example made and is got by mocvd method;
With the heating rate of 50 ℃/sec, heat III family metal nitride or II-VI compound semiconductor film that an above-mentioned P type mixes, make temperature be climbed to 400-1000 ℃, and in less than 1 minute, keep said temperature by room temperature;
With 12 ℃/sec rate of temperature fall, temperature is reduced to below 400 ℃ fast by said temperature, and above-mentioned P type doped with II I family's metal nitride or II-VI compound semiconductor film are activated into III family metal nitride or the II-VI compound semiconductor film that the 2nd P type mixes; Continue the cooling operation, make temperature roll back room temperature; Wherein, in the process of variations in temperature, temperature was not less than 1 minute greater than 400 ℃ time, less than 10 minutes; The III family metal nitride that above-mentioned the 2nd P type mixes or the resistance of II-VI compound semiconductor film are lower than III family metal nitride or the II-VI compound semiconductor film that an above-mentioned P type mixes.
III family metal nitride that the one P type mixes or II-VI compound semiconductor film are to use Metalorganic chemical vapor deposition method, molecular beam epitaxy to grow up or the halide chemical vapour deposition (CVD) is made and got.
The material of the III family metal nitride film that the one P type mixes is selected certainly: gallium nitride, aluminum indium nitride, aluminium gallium nitride alloy or aluminum indium gallium nitride.
The general formula of this III family metal nitride is: Al
xGa
yIn
1-x-yN, wherein, 0≤x≤1,0≤y≤1.
Its p type impurity of the III family metal nitride film that the one P type mixes is selected certainly: at least a in beryllium, magnesium, calcium, barium, cadmium or the zinc element.
Attention: required according to what use, when temperature is climbed to 400-1000 ℃ by room temperature, promptly hold the temperature operation, hold in the temperature time one and (hold the temperature time) less than 1 minute, temperature is remained in 400-1000 ℃.Afterwards, lower the temperature again.
Major advantage of the present invention is to have the mode of utilizing quick heating-cooling to reach P type dopant activation, heat treatment period is shortened, and then reduce the diffusion problem that long heat treatment is derived.
Further specify below in conjunction with preferred embodiment and accompanying drawing.
Description of drawings
Fig. 1 is the employed temperature gradient curve figure of the inventive method;
Fig. 2 is a graph of a relation of holding temperature time and hole (charge carrier) concentration of the present invention;
Fig. 3 is the graph of a relation of annealing temperature of the present invention and P type gallium nitride film resistance.
Embodiment
Consulting Fig. 1-Fig. 3, for simplicity's sake, below is example with P type gallium nitride film only, with the actuating force that explanation the present invention uses fast temperature to change, P type high value film is activated into the method for P type low resistance film.Yet the present invention is not limited to activate P type gallium nitride film, every III family's metal nitride (III-Nitride), and as InGaN (InGaN), aluminum indium nitride (InAlN), aluminium gallium nitride alloy (AlGaN), aluminum indium gallium nitride etc., its general formula is (Al
xGa
yIn
1-x-yN), wherein, 0≤x≤1,0≤y≤1; And the II-VI compounds of group, as ZnSe, ZnMgSe etc., formed P type film all can be used method of the present invention and reduce its resistance.
The present invention mainly provides the manufacture method that a kind of gallium nitride film with high-resistance P type doping activates into the low-resistance P type gallium nitride film, and it is all applicable to comprise individual layer, Bulk P type gallium nitride and homogeneity or heterojunction structure.
Fig. 1 shows the employed temperature gradient curve figure of the inventive method.Below will consult Fig. 1, describe method of the present invention in detail.
According to the present invention the high-resistance P type gallium nitride film is activated into the manufacture method of low-resistance P type gallium nitride film, comprises step as described below:
At first, the gallium nitride film that provides a P type to mix uses mocvd method to make and get; Because the p type impurity of the gallium nitride film that mixes, 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, so the gallium nitride film that causes an above-mentioned P type to mix can present the high value state unavoidablely.
Wherein, the gallium nitride film that an above-mentioned P type mixes also can use molecular beam epitaxy (MBE) or halide chemical gaseous phase epitaxy (HVPE) to make and get.
Then, (for example: R1＞50 ℃/sec), heat the gallium nitride film that an above-mentioned P type mixes make temperature be climbed to first specified temp (being not less than 400 ℃) by initial temperature (being about 27 ℃ of room temperatures) with suitable heating rate R1; At present embodiment, above-mentioned first specified temp is 1000 ℃.
(for example R2:12 ℃/sec), make temperature drop to second specified temp fast by above-mentioned first specified temp (1000 ℃) is 400 ℃ in this embodiment with suitable rate of temperature fall R2.The gallium nitride film that an above-mentioned P type mixes then is activated into the 2nd P type gallium nitride film.
Continue cooling, make temperature get back to above-mentioned initial temperature.The speed of cooling can be contrasted above-mentioned rate of temperature fall, also or with other speed be carried out; In speed that present embodiment adopted less than above-mentioned rate of temperature fall.
Consult Fig. 1, when temperature rises to first specified temp (1000 ℃), continue to allow above-mentioned first specified temp keep a special time T1 (promptly holding the temperature time), just implement cooling afterwards with specific rate of temperature fall R2.Above-mentioned special time T1 must be less than 1 minute; In the present embodiment, T1 was less than 25 seconds.In addition, no matter hold the length of warm time T 1, in the process of variations in temperature, temperature must be not less than 1 minute greater than the time (T2) of above-mentioned second specified temp (400 ℃), less than 10 minutes.
The present invention mainly utilizes rising suddenly of temperature plunge (high-temperature gradient), P type in the moment gallium nitride film that an above-mentioned P type mixed with the actuating force (driving force) of high-temperature gradient or the energy that makes moment mixes (for example Mg) and the bond of hydrogen interrupts, to discharge the doping charge carrier of P type; Gallium nitride film activation becoming the 2nd P type gallium nitride film with above-mentioned P type doping.
Because the P type carrier concentration that has in the 2nd P type gallium nitride film is higher than the gallium nitride film that a P type mixes, so the resistance of the 2nd P type gallium nitride film is lower than the gallium nitride film that a P type mixes.
Fig. 2 shows and to hold temperature time (T1) and hole concentration (curve a) and the relation of mobility (curve b).By Fig. 2 curve a as can be known, holding temperature is lower than 10 seconds and can obtains hole concentration be higher than 4 * 10 the time
17Cm
-3Along with the increase (greater than 10 seconds) of time, not only not increase of hole concentration, successively decrease in time on the contrary.By Fig. 2 curve b as can be known, hold temperature and the time be lower than 10 seconds, its mobility is lower; Along with the increase (greater than 10 seconds) of time, mobility also and then increases.
Therefore, when temperature rises to 1000 ℃, the present invention can select to continue to hold temperature time (T1) less than 1 minute, or did not hold temperature (T1=0) and directly lower the temperature, and all can make the P type gallium nitride film of activation have the carrier concentration that meets demand and (for example be higher than 4 * 10
17Cm
-3), and reduce its resistance.
Fig. 3 shows the relation of short annealing temperature and P type gallium nitride film resistance.As shown in Figure 3, the time be fixed as under 10 seconds the situation when holding temperature, the temperature that is kept is more than or equal to 1000 ℃ the time, and P type gallium nitride film has quite low 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 (as above-mentioned) that adopts Ri Ya chemical company to be proposed.But Ri Ya chemical company carries out the condition of thermal annealing, must be full of under nitrogen or other inert gas environments, and (be generally 700 ℃) between design temperature 400-1200 ℃, and hold temperature more than 1 minute.Yet as mentioned above, if add the time of heating up and lowering the temperature, the process of whole annealing can surpass more than 10 minutes, so P type gallium nitride film may produce diffusion problem because of long heat treatment, produce diffusion problem at different layers, and then influence its usefulness performance.
Hold the temperature time less than 1 minute owing to of the present invention, or can not hold temperature, and be to utilize the mode of quick heating-cooling to reach the purpose of activation, even if so be used in the application of heterojunction or light-emitting diode, the diffusion that the variation that each composition of layer of P type gallium nitride film is formed or composition surface (junction) mix, all can be because of heat treatment period shorten, and reduce the diffusion problem that long heat treatment produced.
Though the present invention discloses as above with preferred embodiment, so it is not in order to limiting the present invention, anyly is familiar with this skill person, and without departing from the spirit and scope of the present invention, a little change and the retouching done is all within protection scope of the present invention.
Claims (5)
1, a kind of the high-resistance P type film is activated into the manufacture method of low-resistance P type film, it is characterized in that: it comprises following step:
The III family metal nitride or the II-VI compound semiconductor film that provide a P type to mix;
With the heating rate of 50 ℃/sec, heat III family metal nitride or II-VI compound semiconductor film that an above-mentioned P type mixes, make temperature be climbed to 400-1000 ℃, and in less than 1 minute, keep said temperature by room temperature;
With 12 ℃/sec rate of temperature fall, temperature is reduced to below 400 ℃ fast by said temperature, and above-mentioned P type doped with II I family's metal nitride or II-VI compound semiconductor film are activated into III family metal nitride or the II-VI compound semiconductor film that the 2nd P type mixes;
Continue the cooling operation, make temperature roll back room temperature;
Wherein, in the process of variations in temperature, temperature was not less than 1 minute greater than 400 ℃ time, less than 10 minutes; The III family metal nitride that above-mentioned the 2nd P type mixes or the resistance of II-VI compound semiconductor film are lower than III family metal nitride or the II-VI compound semiconductor film that an above-mentioned P type mixes.
2, manufacture method as claimed in claim 1 is characterized in that: III family metal nitride that a P type mixes or II-VI compound semiconductor film are to use Metalorganic chemical vapor deposition method, molecular beam epitaxy to grow up or the halide chemical vapour deposition (CVD) is made and got.
3, manufacture method as claimed in claim 1 is characterized in that: the material of the III family metal nitride film that a P type mixes is selected from: gallium nitride, InGaN, aluminum indium nitride, aluminium gallium nitride alloy or aluminum indium gallium nitride.
4, manufacture method as claimed in claim 1 is characterized in that: the general formula of this III family metal nitride is: Al
xGa
yIn
1-x-yN, wherein, 0≤x≤1,0≤y≤1.
5, manufacture method as claimed in claim 1 is characterized in that: III family its p type impurity of metal nitride film that a P type mixes is selected from: at least a in beryllium, magnesium, calcium, barium, cadmium or the zinc element.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011090324A CN1158697C (en) | 2001-02-27 | 2001-02-27 | Method for activating hihg-resistance P type film into low-resistance P type film |
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|---|---|---|---|
| CNB011090324A CN1158697C (en) | 2001-02-27 | 2001-02-27 | Method for activating hihg-resistance P type film into low-resistance P type film |
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| CN1158697C true CN1158697C (en) | 2004-07-21 |
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| CN109285774B (en) * | 2018-09-12 | 2023-03-24 | 江苏能华微电子科技发展有限公司 | Junction barrier Schottky diode based on gallium nitride and forming method thereof |
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