CN110055502B - A kind of preparation method of semiconductor boron carbon film with adjustable band gap - Google Patents
A kind of preparation method of semiconductor boron carbon film with adjustable band gap Download PDFInfo
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- CN110055502B CN110055502B CN201910374278.8A CN201910374278A CN110055502B CN 110055502 B CN110055502 B CN 110055502B CN 201910374278 A CN201910374278 A CN 201910374278A CN 110055502 B CN110055502 B CN 110055502B
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 20
- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052796 boron Inorganic materials 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 5
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 5
- 239000010409 thin film Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000012237 artificial material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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Abstract
本发明的一种带隙可调的半导体硼碳薄膜的制备方法属于非晶半导体薄膜材料制备的技术领域。在磁控溅射设备上以玻璃为基底材料，使用高纯的硼靶和碳靶，基底与靶材间的距离均是55mm，以氩气为工作气体，在1.0Pa工作气压下，控制硼靶功率在160W～240W变化、碳靶功率在50W～80W变化、基底温度在200～400℃变化，进行磁控溅射，得到带隙不同的半导体硼碳薄膜。本发明利用磁控溅射方法，通过对基底温度、硼靶功率和碳靶功率的控制，有效调控了a‑C:B中碳原子的sp2杂化态和sp3杂化态的比例含量，最终探索出一种有效调控a‑C:B的Eopt的方法，为进一步开发可应用的a‑C具有重要意义。
The invention relates to a preparation method of a semiconductor boron-carbon thin film with adjustable band gap, which belongs to the technical field of the preparation of amorphous semiconductor thin film materials. On the magnetron sputtering equipment, glass is used as the base material, high-purity boron target and carbon target are used, the distance between the base and the target is 55mm, argon is used as the working gas, and the boron is controlled under the working pressure of 1.0Pa. The target power is varied from 160W to 240W, the carbon target power is varied from 50W to 80W, and the substrate temperature is varied from 200 to 400°C. Magnetron sputtering is performed to obtain semiconductor boron-carbon films with different band gaps. The invention utilizes the magnetron sputtering method to effectively control the proportion content of the sp 2 hybrid state and the sp 3 hybrid state of carbon atoms in a-C:B by controlling the substrate temperature, the power of the boron target and the power of the carbon target. , and finally explored a method to effectively regulate the E opt of a-C:B, which is of great significance for the further development of applicable a-C.
Description
Technical Field
The invention belongs to the technical field of amorphous semiconductor film material preparation, and particularly relates to a preparation method of a semiconductor boron-carbon film with adjustable band gap.
Background
The amorphous carbon thin films (a-C) have a wide optical band gap (E)opt) The material is a potential novel semiconductor material and has wide application value in the aspects of electrical, mechanical, optical, thermal, chemical and thermal stability and the like. Such as excellent mechanical property, so that a-C is already applied to various wear-resistant coatings and lightsThe window learning device has wide application in the aspects of window learning, wear-resistant magnetic memory devices and the like; in the aspect of electricity, a-C can be used for preparing large-scale integrated circuits, solar cells and the like; in biomedicine, the a-C can be plated on an artificial material and implanted into a living body to promote the compatibility between the artificial material and the tissues of the living body. However, due to the disordered structure of a-C, E is regulated and controlled through experimental meansoptIt is difficult. At present, a-C is changed into a semiconductor film with controllable band gap by doping element (B, N, P) mostly, and E is controlled by controlling the content of the doping elementoptHowever, the content and distribution of the doping elements are difficult to control. Therefore, the method for controllably preparing the a-C with adjustable band gap is important to be explored.
In a-C, it is decided that E isoptThe essential origin of (A) is sp of a carbon atom2Hybrid state and sp3Proportional content of hybrid states, sp2Pi electrons in the hybrid state are important factors in providing carriers and forming a hopping conduction mechanism. Thus regulating sp2And sp3The proportion content of the hybrid state is an effective method for achieving adjustable a-C band gap. The E of a-C can be effectively adjusted by doping boronoptCurrently, the focus is mainly on the study of changing the boron content to regulate Eopt. But how to control E by changing experimental conditionsoptNo report is found.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the background technology and adjust the A-C E by various modes by changing the deposition parameters of magnetron sputteringopt. The film synthesized by the method has the advantages of high deposition rate, wide band gap adjustable range, repeatable experiment, simple instrument operation and lower cost.
The specific technical scheme of the invention is as follows.
A preparation method of a band gap adjustable semiconductor boron-carbon film is characterized in that on a magnetron sputtering device, glass is used as a substrate material, a boron target and a carbon target with the purity of 99.999% are used, the distance between the substrate and the target is 55mm, argon is used as working gas, under the working pressure of 1.0Pa, the power of the boron target is controlled to be changed from 160W to 240W, the power of the carbon target is controlled to be changed from 50W to 80W, and the temperature of the substrate is controlled to be changed from 200 ℃ to 400 ℃, and the semiconductor boron-carbon film with different band gaps is obtained through magnetron sputtering.
The preferred scheme of the invention is to maintain the working pressure of 1.0Pa and the substrate temperature of 200 ℃, control the carbon target power to be 50W, and control the boron target power to be 160W-240W, so as to obtain the semiconductor boron-carbon film with the band gap range of 3.19 eV-2.78 eV.
Another preferred scheme of the invention is to maintain the working pressure of 1.0Pa and the substrate temperature of 200 ℃, control the boron target power of 160W and the carbon target power to be changed between 50W and 80W, and obtain the semiconductor boron-carbon film with the band gap ranging from 3.19eV to 2.90 eV.
The experiments of the invention are all completed on JGP450 type radio frequency magnetron sputtering equipment, and the a-C: B with adjustable band gap is successfully prepared. The invention utilizes the magnetron sputtering method, and effectively regulates and controls the sp of carbon atoms in the boron-doped amorphous carbon film (a-C: B) by controlling the substrate temperature, the boron target power and the carbon target power2Hybrid states and sp3The proportion content of the hybrid state finally explores the E which can effectively regulate and control a-C: BoptThe method has important significance for further developing the applicable a-C.
Has the advantages that:
1. the invention realizes Eo of the semiconductor boron-carbon film by respectively changing the substrate temperature, the boron target power and the carbon target powerptThe controllability is good.
2. The film prepared by the method has high deposition rate.
3. The invention takes cheap glass as a substrate to directly synthesize a-C: B, and the preparation method is simple.
Drawings
FIG. 1 is E of a-C: B prepared by varying boron target power in example 1optFigure (a).
FIG. 2 is a graph of X-ray photoelectron spectroscopy measurements of a-C: B prepared by varying the boron target power in example 1.
FIG. 3 is E of a-C: B prepared by varying the carbon target power in example 2optFigure (a).
FIG. 4 is a graph showing the temperature of a substrate changed in example 3Preparation of E of a-C: BoptFigure (a).
FIG. 5 is E of a-C: B prepared by varying the working air pressure in example 4optFigure (a).
Detailed Description
Example 1
Glass is selected as a substrate material, the purity of a boron target and the purity of a carbon target are both 99.999 percent, the distance between the substrate and the target is both 55mm, and the working gas is argon. The power of the carbon target is fixed to be 50W; the substrate temperature is 200 ℃; the working air pressure is 1.0 Pa; controlling the power of the boron target to be 160W, 200W and 240W respectively, and carrying out magnetron sputtering on JGP450 type radio frequency magnetron sputtering equipment. E of the product preparedoptThe figure is shown in figure 1: e of the film with increasing boron target poweroptVarying from 3.19eV to 2.78 eV. Therefore, the phenomenon that the band gap of the film is reduced in a monotonous way along with the increase of the target power proves that the E of the film can be effectively regulated and controlled by regulating and controlling the boron target poweroptAnd has the advantage of wide regulation and control range.
The prepared sample was subjected to X-ray photoelectron spectroscopy, and the results are shown in fig. 2. When the boron target power was increased to 240W, a new peak 283.2eV (B-C) appeared, representing the boron atom build-up with the carbon atom, due to: as the boron target power is increased, the interaction of the doped boron with the carbon atoms is enhanced. And the peak position on the carbon atom is 284.1eV (sp) as the power of the boron target is increased2) And 284.9eV (sp)3) The area ratio of (A) to (B) is also increased, and the two peaks respectively represent sp of carbon atoms2Hybrid states and sp3The hybrid state. This indicates that increasing the boron target power can cause sp of carbon atoms in the film2The hybrid state increases. sp2The increase of the hybrid state is to make the thin film EoptThe essential reason for the reduction.
Example 2
The fixed boron target power is 160W; regulating the power of the carbon target to be 50W, 60W and 80W respectively; the other conditions were the same as in example 1. Sample E thus obtainedoptThe figure is shown in figure 3: e of the film with increasing carbon target poweroptVarying from 3.19eV to 2.90 eV. Therefore, the E of the film can be effectively regulated and controlled by regulating and controlling the power of the carbon targetoptAnd the regulation and control range is still larger.
Example 3
The same substrate, target material, target substrate distance, and working gas as in example 1 were used. Adjusting the substrate temperature to 200 ℃, 300 ℃ and 400 ℃ respectively; the working air pressure is 1.0 Pa; the boron target power is 160W; the carbon target power was 50W. E of the prepared sampleoptAs shown in fig. 4. The results show that: e of the film with increasing substrate temperatureoptIs gradually decreased, EoptThe regulation range of (A) is 3.19eV-3.15 eV. Thus E of the film can also be adjusted by adjusting the substrate temperatureoptBut the band gap range of the adjustment is narrow.
Example 4
The same substrate, target material, target substrate distance, and working gas as in example 1 were used. Changing the working air pressure to 1.0Pa, 1.5Pa and 2.0 Pa; the substrate temperature is 200 ℃; the carbon target power is 50W; the boron target power was 160W. E of the prepared sampleoptAs shown in FIG. 5, the E of the film changes with the change of the working air pressureoptThe law of decreasing first and increasing second appears, which shows that the effective control E that the working air pressure is difficult to monotonically increase or monotonically decreaseoptA change in (c). This example is a counter example, used to compare the effects produced by the protocol of the present invention.
From the above examples, it can be seen that the deposition parameters of the present invention comprehensively affect EoptThe value needs to be considered comprehensively, wherein the most influential factor is the target power, and the target power is adjusted by EoptCan be controlled by a single adjustment and has a large control range, EoptThe value can be reduced from 3.19eV to 2.78 eV. The essential reason is that the sp in the film is caused along with the increase of the target power2Content of hybrid state, thereby E of the filmoptAnd decreases.
Claims (3)
1. A preparation method of a band gap adjustable semiconductor boron-carbon film is characterized in that on a magnetron sputtering device, glass is used as a substrate material, a boron target and a carbon target with the purity of 99.999% are used, the distance between the substrate and the target is 55mm, argon is used as working gas, under the working pressure of 1.0Pa, the power of the boron target is controlled to be changed from 160W to 240W, the power of the carbon target is controlled to be changed from 50W to 80W, and the temperature of the substrate is controlled to be changed from 200 ℃ to 400 ℃, and the semiconductor boron-carbon film with different band gaps is obtained through magnetron sputtering.
2. The method for preparing the semiconductor boron-carbon film with the adjustable band gap according to claim 1, wherein the working pressure of 1.0Pa and the substrate temperature of 200 ℃ are maintained, the carbon target power is controlled to be 50W, and the boron target power is controlled to be changed from 160W to 240W, so that the semiconductor boron-carbon film with the band gap ranging from 3.19eV to 2.78eV is obtained.
3. The method for preparing the semiconductor boron-carbon film with the adjustable band gap according to claim 1, wherein the working pressure of 1.0Pa and the substrate temperature of 200 ℃ are maintained, the boron target power is controlled to be 160W, and the carbon target power is changed from 50W to 80W, so that the semiconductor boron-carbon film with the band gap ranging from 3.19eV to 2.90eV is obtained.
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| CN110670017B (en) * | 2019-10-22 | 2021-05-18 | 浙江大学 | A band gap control method in the preparation of hexagonal boron nitride thin films |
| CN113969393A (en) * | 2021-10-29 | 2022-01-25 | 江苏华兴激光科技有限公司 | Amorphous carbon film with adjustable band gap and preparation method thereof |
Citations (2)
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| CN101246926A (en) * | 2007-02-14 | 2008-08-20 | 北京行者多媒体科技有限公司 | Amorphous boron-carbon alloy and photovoltaic application thereof |
| CN101403098A (en) * | 2008-11-05 | 2009-04-08 | 湖北大学 | Magnetic memory material of compound structure of FePt nano-particle monolayer film and B4C and method of producing the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101246926A (en) * | 2007-02-14 | 2008-08-20 | 北京行者多媒体科技有限公司 | Amorphous boron-carbon alloy and photovoltaic application thereof |
| CN101403098A (en) * | 2008-11-05 | 2009-04-08 | 湖北大学 | Magnetic memory material of compound structure of FePt nano-particle monolayer film and B4C and method of producing the same |
Non-Patent Citations (2)
| Title |
|---|
| "溅射功率对碳化硼薄膜组分与力学性能的影响";张玲 等;《强激光与粒子束》;20130930;第25卷(第9期);第2317-2323页 * |
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