CN1372307A - Activation method for reducing p type film resistance by laser - Google Patents
Activation method for reducing p type film resistance by laser Download PDFInfo
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- CN1372307A CN1372307A CN01109033A CN01109033A CN1372307A CN 1372307 A CN1372307 A CN 1372307A CN 01109033 A CN01109033 A CN 01109033A CN 01109033 A CN01109033 A CN 01109033A CN 1372307 A CN1372307 A CN 1372307A
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Abstract
A activatino method of reducing the p-type film reuistance value by laser to activate the P-type film with high resistance value to P-type film with low restance value, in which the high resistance value P-type film is the p-type doped 3-group metallic nitride film or p-type doped 2-6 group compound film. The operation of this method is carrier out under the environmental atmosphere directly without special inert gas or to change laser power or focal distance or modulate the power to reduce the activiation time with easy operation and less cost.
Description
The invention relates to a kind of activation method that uses laser light to reduce P type film resistance, particularly activate into the activation method of the low resistance film of P type doping relevant for the film that utilizes laser light with high-resistance P type doping.
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) ... Deng; And the II-VI compounds of group of wide energy gap is as P-ZnSe, ZnMgSe ... Deng, has superior photoelectric characteristic, so above-mentioned material also was made into film shape in recent years widely, was applied on the photoelectric subassembly, for example: light-emitting diode (LEDs) and laser diode (LDs).Yet, when above-mentioned material is made into 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-OrganicChemicalVaporDeposition by the technology of the resilient coating of growing up on the aluminum oxide substrate (buffer layer); Be designated hereinafter simply as mocvd method) the formation gallium nitride film.Gallium nitride film when mixing p type impurity, as: during elements such as beryllium Be, magnesium Mg, calcium Ca, zinc Zn, cadmium Cd, above-mentioned p type impurity is very easy to and the hydrogen 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 electric hole concentration often is lower than 10
12Ω cm
-3, also therefore on using, be severely limited.
The IAkasaki of Japan Nagoya university and HAmano use low energy electrons bundle (LEEBI) treatment with irradiation to be doped with the gallium nitride film of Mg, and its activation is obtained P type gallium nitride film.Yet the method that Nagoya University proposed because active rate is too slow, and has only near the film the activating surface, so and impracticable.
The SNakamura of Ri Ya chemical company then uses two air-flow organic metal gasification phase sedimentations and low temperature gallium nitride resilient coating to come the gallium nitride growth film.Utilize the mode of 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 process conditions of its annealing are under the environment of nitrogen, between temperature 400-1200 ℃, hold temperature more than 1 minute.The activation method of Ri Ya chemical company must carry out being full of under the nitrogen or the environment of other noble gas, can't directly carry out under atmospheric environment, so can increase the cost and the degree of difficulty of making.
The object of the present invention is to provide a kind of method of utilizing laser light the high-resistance P type film to be activated into the low-resistance P type film, wherein, the material of above-mentioned P type high value film is an III family metal nitride (III-Nitride), as gallium nitride (GaN), InGaN (InGaN), aluminium gallium nitride alloy (AlGaN), aluminum indium gallium nitride (AlGaInN) ... Deng; And the II-VI compounds of group is as P-ZnSe, ZnMgSe ... Deng.
Method of the present invention is directly to carry out under atmospheric environment, does not need to carry out under the noble gas environment especially, and can shorten soak time to adjust power density by changing the power and the focal length of laser light.
The object of the present invention is achieved like this: the high-resistance P type film is activated into the activation method of low-resistance P type film, comprise the steps:
The one P type film is provided, for example makes and get by mocvd method;
Use laser light illumination (for example infrared ray laser) on an above-mentioned P type film, provide energy that the bond of doping of P type and hydrogen in the above-mentioned P type film is interrupted, to discharge the carrier that the P type mixes, above-mentioned P type film activation is become the 2nd P type film, make the resistance of above-mentioned the 2nd P type film be lower than an above-mentioned P type gallium nitride film.
Major advantage of the present invention is that method of the present invention can directly be carried out under atmospheric environment, does not need to carry out under the noble gas environment especially, and can shorten soak time to adjust power by changing the power and the focal length of laser light.Have processing procedure and reach the practical effect of saving cost of manufacture easily.
Further specify below in conjunction with preferred embodiment and accompanying drawing.
Fig. 1 is the graph of a relation of laser light power of the present invention and gallium nitride film resistance;
Fig. 2 is the graph of a relation of laser light illumination time of the present invention and gallium nitride film resistance;
Fig. 3 is the graph of a relation of laser light power of the present invention and gallium nitride film carrier concentration;
Fig. 4 is the graph of a relation of laser light illumination time of the present invention and gallium nitride film carrier concentration;
Fig. 5 is the graph of a relation of the ray laser spectrogram of laser light power of the present invention and gallium nitride film;
Fig. 6 is the graph of a relation of laser light illumination time of the present invention and gallium nitride film carrier concentration.
Consulting Fig. 1-Fig. 6, for simplicity's sake, below is example with P type gallium nitride film only, and the present invention uses laser light P type high value film to be activated into the method for P type low resistance film with explanation.Yet the present invention is not limited to activate P type gallium nitride film, and every III family's metal nitride (III-Nitride) is as InGaN (InGaN), aluminium gallium nitride alloy (AlGaN), aluminum indium gallium nitride (AlGaInN) ... Deng; And the II-VI compounds of group is as P-ZnSe, ZnMgSe ... Deng, formed P type film all can be used method of the present invention and reduce its resistance.
The invention provides and a kind of the high-resistance P type gallium nitride film is activated into the manufacture method of low-resistance P type gallium nitride film, it is all applicable to comprise individual layer, Bulk P type gallium nitride and homogeneity or heterojunction structure.
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 following step:
At first, provide a P type gallium nitride film, it is to use mocvd method to make and get; Because the p type impurity of the gallium nitride film that mixes, as: elements such as beryllium Be, magnesium Mg, calcium Ca, zinc Zn, cadmium Cd, hydrogen very easy and in the reacting gas combines, so cause an above-mentioned P type gallium nitride film can present the high value state unavoidablely.Wherein, an above-mentioned P type gallium nitride film also can use molecular beam epitaxy method (MBE) or halide chemical gaseous phase brilliant method (HVPE) of heap of stone to make and get.
Then, use the laser light uniform irradiation on an above-mentioned P type gallium nitride film,, the bond of doping of P type and hydrogen in the above-mentioned P type gallium nitride film can be interrupted, to discharge the carrier that the P type mixes because moment provides high-energy; With above-mentioned P type gallium nitride film activation becoming the 2nd P type gallium nitride film.
Because the P type carrier concentration that has in the 2nd P type gallium nitride film is higher than a P type gallium nitride film, so the resistance of the 2nd P type gallium nitride film is lower than an above-mentioned P type gallium nitride film.In addition, above-mentioned laser light can be selected from gas laser, solid laser or liquid laser ... Deng; In this preferred embodiment, above-mentioned laser light is to use the infrared ray laser light, for example CO2 Lasers light.
Embodiments of the invention mainly are to use the infrared ray laser light illumination on a P type gallium nitride film that is formed by mocvd method, to activate an above-mentioned P type gallium nitride film.The power of infrared ray laser light generally is not more than 50W, but can also use power to be higher than the infrared ray laser light of 50W according to need.
Method of the present invention can be by adjusting power and the infrared ray laser and the P type gallium nitride film distance between the two of infrared ray laser, adjust power density (power density, the W/cm of infrared ray laser light illumination on an above-mentioned P type gallium nitride film
2), and make soak time less than 1 minute.But along with infrared ray laser energy difference and focal length difference, soak time also can also can obtain needed activation results more than 1 minute or 1 minute.
Fig. 1 shows the relation of laser light power and gallium nitride film resistance.As shown in Figure 1, do not accepting infrared ray laser pre-irradiation when a P type gallium nitride film, its film resistance is quite high, has reached the limit of Detecting device; But along with the infrared ray laser power increases, its film resistance also descends gradually, and when power increased to 10W, resistance had dropped to 1,2 Ω cm.
Fig. 2 shows the relation of laser light illumination time and gallium nitride film resistance.As shown in Figure 2, if with infrared ray laser power stuck-at-0W, along with irradiation time increases, its film resistance will descend gradually.When irradiation time was 9 minutes, its resistance dropped to 1,48 Ω cm; If when the time increased to 12 minutes, its resistance dropped to 1,2 Ω cm.
Fig. 3 shows the relation of laser light power and gallium nitride film carrier concentration.Generally speaking, do not accepting infrared ray laser pre-irradiation when a P type gallium nitride film, the concentration of its P type doping carrier is on the low side, is about 10
12Cm
-3, mainly be because of the event of original N type carrier combination in meeting of part P type doping carrier and the gallium nitride film, and the part p type impurity forms the event of bond with hydrogen.But along with laser power increases (as shown in Figure 3), bond in the one P type gallium nitride film between p type impurity and the hydrogen is interrupted by the high power of laser light, therefore there is more P type carrier to disengage, and makes P type gallium nitride film activation becoming the 2nd P type gallium nitride film.P type carrier concentration in the 2nd P type gallium nitride film also increases with the increase of laser light power, and when laser light power increased to 10W, its carrier concentration can reach 7 * 10
17Cm
-3More than.
Fig. 4 shows the relation of laser light illumination time and gallium nitride film carrier concentration.As shown in Figure 4, increase along with the laser light illumination time, laser light has that the time is interrupted the bond between p type impurity and the hydrogen in the P type gallium nitride film more fully, therefore there is more P type carrier to discharge, and makes P type gallium nitride film activation becoming the 2nd P type gallium nitride film.Laser light power is fixed under the situation of 10W, irradiation time was increased to 9 minutes, its carrier concentration can reach 4 * 10
17Cm
-3, if irradiation time was increased to 12 minutes, its carrier concentration can reach 7 * 10
17Cm
-3
Fig. 5 shows the relation of the ray laser spectrogram of laser light power and gallium nitride film.As shown in Figure 5, when a P type gallium nitride film is not being accepted infrared ray laser pre-irradiation (curve I), in its ray laser frequency spectrum, near about 450nm blue light frequency band intensity is considerably little, but along with laser power increases, the intensity of its blue light frequency band also strengthens (curve II, III) relatively, and this result represents that the activation degree that the P type mixes increases and improves along with laser power.
Fig. 6 shows the relation of the ray laser spectrogram of laser light illumination time and gallium nitride film.As shown in Figure 6, be under the situation of 10W at fixing laser light power, along with the laser irradiation time increases, the intensity of its blue light frequency band also strengthens relatively, and this result represents that the activation degree that the P type mixes increases and improves along with laser power.
By the experimental data of above-mentioned Fig. 1-shown in Figure 6 as can be known, to make a P type gallium nitride film with mocvd method with high value, after using activation method of the present invention to handle, really make the resistance of the 2nd P type gallium nitride film after activating reduce, P type carrier wherein increases, and has more stronger blue light frequency response.
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 the nitrogen or the environment of other noble gas, and between design temperature 400-1200 ℃, and hold temperature more than 1 minute.Yet characteristics of the present invention are, can directly use laser light to activate under atmospheric environment, must not carry out under the environment of special gas; And power that can be by adjusting laser light and focal length, and power density shorten soak time.Therefore, activation method of the present invention, than traditional approach, not only processing procedure is easy, can save cost of manufacture, has suitable practicality for opto-electronics.
Though the present invention discloses as above with preferred embodiment, be not in order to limiting the present invention, anyly be familiar with this skill person, without departing from the spirit and scope of the present invention, change of being done and retouching all belong within protection scope of the present invention.
Claims (12)
1, a kind of activation method that uses laser light to reduce P type film resistance, it is characterized in that: it comprises the steps:
The III family metal nitride film that provides a P type to mix;
Use laser light illumination on the III family metal nitride film that an above-mentioned P type mixes, the III family metal nitride film that III family metal nitride film activation becoming the 2nd P type that an above-mentioned P type is mixed mixes; Wherein, the resistance of the III family metal nitride film of above-mentioned the 2nd P type doping is lower than the III family metal nitride film that an above-mentioned P type mixes.
2, activation method as claimed in claim 1 is characterized in that: this laser light is gas laser, solid laser or liquid laser light.
3, activation method as claimed in claim 1 is characterized in that: this laser light is the infrared ray laser light.
4, activation method as claimed in claim 1 is characterized in that: this laser light is an infrared ray CO2 Lasers light.
5, activation method as claimed in claim 1 is characterized in that: the III family metal nitride film that a P type mixes is to use Metalorganic chemical vapor deposition method, molecular beam epitaxy method or halide chemical gaseous phase brilliant manufactured of heap of stone and gets.
6, activation 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, aluminium gallium nitride alloy or aluminum indium gallium nitride.
7, activation method as claimed in claim 1 is characterized in that: the p type impurity of the III family metal nitride film that a P type mixes is selected from: at least a in beryllium, magnesium, calcium, barium, cadmium or the zinc element.
8, a kind of activation method that uses laser light to reduce P type film resistance, it is characterized in that: it comprises the steps:
The II-VI compound semiconductor film that provides a P type to mix;
Use laser light illumination on the II-VI compound semiconductor film that an above-mentioned P type mixes, the II-VI compound semiconductor film that II-VI compound semiconductor film activation becoming the 2nd P type that an above-mentioned P type is mixed mixes; Wherein, the resistance of the II-VI compound semiconductor film of above-mentioned the 2nd P type doping is lower than the II-VI compound semiconductor film that an above-mentioned P type mixes.
9, activation method as claimed in claim 8 is characterized in that: this laser light is gas laser, solid laser or liquid laser light.
10, activation method as claimed in claim 8 is characterized in that: this laser light is the infrared ray laser light.
11, activation method as claimed in claim 8 is characterized in that: this laser light is an infrared ray CO2 Lasers light.
12, activation method as claimed in claim 8 is characterized in that: the II-VI compound semiconductor film that a P type mixes is to use Metalorganic chemical vapor deposition method, molecular beam epitaxy method or halide chemical gaseous phase brilliant manufactured of heap of stone and gets.
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| CNB011090332A CN1140919C (en) | 2001-02-27 | 2001-02-27 | Activation method for reducing p type film resistance by laser |
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| CNB011090332A CN1140919C (en) | 2001-02-27 | 2001-02-27 | Activation method for reducing p type film resistance by laser |
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| CN1140919C CN1140919C (en) | 2004-03-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357486C (en) * | 2005-11-10 | 2007-12-26 | 复旦大学 | Process for preparing film material by unbalanced normal positional mixing |
| CN106252216A (en) * | 2016-09-21 | 2016-12-21 | 中国科学院合肥物质科学研究院 | Use the method that laser irradiation gallium nitride epitaxial slice improves its ohmic contact characteristic |
-
2001
- 2001-02-27 CN CNB011090332A patent/CN1140919C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357486C (en) * | 2005-11-10 | 2007-12-26 | 复旦大学 | Process for preparing film material by unbalanced normal positional mixing |
| CN106252216A (en) * | 2016-09-21 | 2016-12-21 | 中国科学院合肥物质科学研究院 | Use the method that laser irradiation gallium nitride epitaxial slice improves its ohmic contact characteristic |
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|---|---|
| CN1140919C (en) | 2004-03-03 |
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