CN110517950A - A method of preparing Zinc-Blende GaN film on a diamond substrate - Google Patents
A method of preparing Zinc-Blende GaN film on a diamond substrate Download PDFInfo
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 57
- 239000010432 diamond Substances 0.000 title claims abstract description 57
- 239000000758 substrate Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229910052984 zinc sulfide Inorganic materials 0.000 title abstract description 7
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims abstract description 9
- 230000006911 nucleation Effects 0.000 claims description 27
- 238000010899 nucleation Methods 0.000 claims description 27
- 229910052950 sphalerite Inorganic materials 0.000 claims description 22
- 239000010408 film Substances 0.000 claims description 16
- 239000010409 thin film Substances 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000012792 core layer Substances 0.000 abstract 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 8
- 230000005693 optoelectronics Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- IGELFKKMDLGCJO-UHFFFAOYSA-N xenon difluoride Chemical compound F[Xe]F IGELFKKMDLGCJO-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000005701 quantum confined stark effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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Abstract
Description
技术领域technical field
本发明属于GaN薄膜制备技术领域，具体涉及一种在金刚石衬底上制备闪锌矿GaN薄膜的方法。The invention belongs to the technical field of GaN thin film preparation, and in particular relates to a method for preparing zinc blende GaN thin film on a diamond substrate.
背景技术Background technique
闪锌矿GaN是一种非极性结构半导体材料，不存在自发极化，因此由其制备的外延发光结构能够避免发生量子限制斯塔克效应。其次，与纤锌矿GaN结构相比，闪锌矿GaN结构的带隙较窄，只需要掺杂少量的铟，就能实现绿光发射，有利于解决目前全彩LED中绿光光效低即“绿隙”问题。Sphalerite GaN is a non-polar semiconductor material without spontaneous polarization, so the epitaxial light-emitting structure prepared from it can avoid the quantum-confined Stark effect. Secondly, compared with the wurtzite GaN structure, the band gap of the sphalerite GaN structure is narrower, and only a small amount of indium needs to be doped to achieve green light emission, which is conducive to solving the low green light efficiency of current full-color LEDs. This is the "green gap" problem.
随着GaN基材料制作的光电功率器件向更小尺寸、更大输出功率和更高频率的方向发展，“热”的问题越来越突出，逐渐成为制约这种器件向更高性能提升的瓶颈。金刚石具有优异的热学性质，其热导率值达2000W/m.K。采用高热导率金刚石作为高频、大功率GaN基器件的衬底或热沉，可以降低GaN基大功率器件的自加热效应，并有望解决随总功率增加、频率提高出现的功率密度迅速下降的问题。2003年，Felix Ejeckam通过将在硅衬底上生长的GaN外延层转移至化学气相沉积合成的金刚石衬底上，首次实现了金刚石基氮化镓；但其使用的制备方法比较繁杂，工艺成本高。2009年，宋明等人在专利中提出了以金刚石为衬底的LED结构，但他们并未提出具体的制备方法。2013年，沈阳工程学院的张东等人提出了采用电子回旋共振-等离子体增强金属有机化学气相沉积（ECR-PEMOCVD）系统制备InN/GaN/金刚石结构。With the development of optoelectronic power devices made of GaN-based materials in the direction of smaller size, higher output power and higher frequency, the problem of "heat" has become more and more prominent, and has gradually become a bottleneck restricting the improvement of such devices to higher performance. . Diamond has excellent thermal properties, and its thermal conductivity reaches 2000W/m.K. Using diamond with high thermal conductivity as the substrate or heat sink of high-frequency and high-power GaN-based devices can reduce the self-heating effect of GaN-based high-power devices, and is expected to solve the problem of rapid decline in power density as the total power increases and the frequency increases. question. In 2003, Felix Ejeckam realized GaN-on-diamond for the first time by transferring the GaN epitaxial layer grown on the silicon substrate to the diamond substrate synthesized by chemical vapor deposition; however, the preparation method used is relatively complicated and the process cost is high . In 2009, Song Ming and others proposed a diamond-based LED structure in their patent, but they did not propose a specific preparation method. In 2013, Zhang Dong et al. from Shenyang Institute of Engineering proposed the preparation of InN/GaN/diamond structures by electron cyclotron resonance-plasma enhanced metal-organic chemical vapor deposition (ECR-PEMOCVD) system.
发明内容Contents of the invention
本发明的目的是解决上述技术中存在的不足，提供了一种在金刚石衬底上制备闪锌矿GaN薄膜的方法。The purpose of the present invention is to solve the deficiencies in the above-mentioned technologies and provide a method for preparing sphalerite GaN thin film on a diamond substrate.
本发明由如下技术方案实现的：一种在金刚石衬底上制备闪锌矿GaN薄膜的方法，先对金刚石衬底用XeF2等离子体进行氟化处理，处理后的金刚石表面形成C-F键，C-F键作为形核位点；然后将金刚石衬底置于MOCVD反应室内生长GaN形核层，再对形核层退火处理，最后合并生长形成闪锌矿GaN薄膜。The present invention is realized by the following technical scheme: a method for preparing sphalerite GaN film on a diamond substrate, firstly, the diamond substrate is fluorinated with XeF2 plasma, and the treated diamond surface forms a CF bond, CF bond as the nucleation site; then the diamond substrate is placed in the MOCVD reaction chamber to grow the GaN nucleation layer, and then the nucleation layer is annealed, and finally merged and grown to form a sphalerite GaN film.
具体步骤如下：Specific steps are as follows:
（1）氟化处理金刚石衬底：金刚石衬底氟化处理的压力为20-100 mbar，功率为100-300mW，用XeF2等离子体处理150-250 s；处理后金刚石表面形成C-F键，作为形核位点，使GaN在金刚石表面形核；(1) Fluorination treatment of diamond substrate: the pressure of diamond substrate fluorination treatment is 20-100 mbar, the power is 100-300mW, and it is treated with XeF 2 plasma for 150-250 s; after treatment, CF bonds are formed on the diamond surface, as Nucleation sites to nucleate GaN on the diamond surface;
（2）生长GaN形核层：金刚石衬底放入MOCVD反应室中，在1200℃的温度，120-200 mbar压力下， H2气氛中进行清洗步骤10-15 min；清洗后，降温至 500-650℃，400-600 mbar下，通入NH3和三甲基镓（TMGa）， V/III比为600-800，生长时间为200-300 s，获得致密形核层；(2) Growth of GaN nucleation layer: Put the diamond substrate into the MOCVD reaction chamber, and perform the cleaning step at a temperature of 1200°C and a pressure of 120-200 mbar in an H 2 atmosphere for 10-15 minutes; after cleaning, cool down to 500 -650°C, 400-600 mbar, feed NH 3 and trimethylgallium (TMGa), V/III ratio 600-800, growth time 200-300 s, to obtain a dense nucleation layer;
（3）退火处理：升温至1100-1200℃，300-450 mbar下，NH3为退火气氛，对GaN形核层进行高温退火2-6 min；(3) Annealing treatment: heat up to 1100-1200°C, under 300-450 mbar, NH 3 is the annealing atmosphere, and perform high-temperature annealing on the GaN nucleation layer for 2-6 minutes;
（4）生长闪锌矿GaN薄膜：温度1050-1150℃，压力100-150 mbar下，通入NH3和TMGa， V/III比为300-800，合并生长GaN薄膜，生长时间为2-3 h。(4) Growth of sphalerite GaN film: temperature 1050-1150°C, pressure 100-150 mbar, feed NH 3 and TMGa, V/III ratio is 300-800, grow GaN film together, growth time is 2-3 h.
本发明具有以下有益效果：The present invention has the following beneficial effects:
LED光电器件在高功率和高频率下运行时，由散热不足会造成器件的光效降低和寿命缩短。金刚石具有高的热导率，当光电器件选用金刚石作为热沉衬底时，散热不足的问题会得以有效克服。本发明以金刚石作为热沉衬底生长闪锌矿GaN薄膜，一方面为进一步制备闪锌矿GaN基薄膜材料的光电器件奠定了基础，有利于解决目前全彩LED中绿光光效低的问题；另一方面也解决了光电器件在高功率、高频率运作下的散热问题。When LED optoelectronic devices operate at high power and high frequency, insufficient heat dissipation will reduce the light efficiency and shorten the life of the device. Diamond has high thermal conductivity. When optoelectronic devices use diamond as a heat sink substrate, the problem of insufficient heat dissipation can be effectively overcome. The present invention uses diamond as a heat sink substrate to grow sphalerite GaN thin films, on the one hand, it lays the foundation for further preparation of optoelectronic devices based on sphalerite GaN thin film materials, and helps to solve the problem of low green light efficiency in current full-color LEDs ; On the other hand, it also solves the heat dissipation problem of optoelectronic devices under high power and high frequency operation.
附图说明Description of drawings
图1为本发明金刚石衬底制备闪锌矿GaN薄膜生长过程的示意图。Fig. 1 is a schematic diagram of the growth process of sphalerite GaN film prepared on a diamond substrate of the present invention.
图2 实施例1样品表面的AFM像。Fig. 2 AFM image of the sample surface of Example 1.
图3 实施例1样品的X射线衍射图（XRD）。Fig. 3 X-ray diffraction pattern (XRD) of the sample of Example 1.
具体实施方式Detailed ways
下文中，将参照附图更充分地描述本发明，附图显示了各种实施例的工艺流程，本发明可以以不同的形式来实施，不局限于在此阐述的实施例。相反，提供这些实施例使得本发明是彻底和完全的，并将本发明充分地传达给本领域的技术人员。下面将参照附图结合实施例更具体地描述本发明。Hereinafter, the present invention will be described more fully with reference to the accompanying drawings, which show process flows of various embodiments, and the invention can be embodied in different forms and is not limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the invention to those skilled in the art. Hereinafter, the present invention will be described more specifically in conjunction with embodiments with reference to the accompanying drawings.
实施例1：一种在金刚石衬底上制备闪锌矿GaN薄膜的方法，先对金刚石衬底用XeF2等离子体进行氟化处理，处理后的金刚石表面形成C-F键，C-F键作为形核位点；然后将金刚石衬底置于MOCVD反应室内生长GaN形核层，再对形核层退火处理，最后合并生长形成闪锌矿GaN薄膜。具体步骤如下：Example 1: A method for preparing a sphalerite GaN film on a diamond substrate. First, the diamond substrate is fluorinated with XeF2 plasma, and CF bonds are formed on the treated diamond surface, and the CF bonds are used as nucleation sites point; then put the diamond substrate in the MOCVD reaction chamber to grow the GaN nucleation layer, then anneal the nucleation layer, and finally merge and grow to form a sphalerite GaN thin film. Specific steps are as follows:
1）氟化处理金刚石衬底：对金刚石衬底进行氟化处理，氟化处理的压力设置为50mbar，功率为100 mW，用XeF2等离子体处理150s。1) Fluorination treatment of diamond substrate: Fluorination treatment was performed on the diamond substrate, the pressure of the fluorination treatment was set at 50 mbar, the power was 100 mW, and XeF 2 plasma was used for 150 s.
2）生长GaN形核层：将金刚石衬底放入MOCVD反应室中，在1200℃的温度，150 mbar压力下， H2气氛中进行清洗步骤10 min。清洗步骤之后，降温至 500℃，400 mbar压力下在金刚石衬底表面生长GaN形核层，通入NH3和TMGa，流量分别为20000 μmol/min，30 μmol/min， V/III比为600，生长时间为200s。2) Growth of GaN nucleation layer: Put the diamond substrate into the MOCVD reaction chamber, and perform the cleaning step for 10 min at a temperature of 1200 ° C, a pressure of 150 mbar, and an H 2 atmosphere. After the cleaning step, the temperature was lowered to 500°C, and a GaN nucleation layer was grown on the surface of the diamond substrate under a pressure of 400 mbar, and NH 3 and TMGa were fed at the flow rates of 20,000 μmol/min and 30 μmol/min, respectively, and the V/III ratio was 600 , the growth time is 200s.
3）退火处理：升温至1100℃，300mbar下对GaN形核层进行高温退火4 min，退火时通入的NH3流量为360000 μmol/min。3) Annealing treatment: heat up to 1100°C, and perform high-temperature annealing on the GaN nucleation layer at 300mbar for 4 minutes, and the flow rate of NH 3 introduced during annealing is 360,000 μmol/min.
4) 生长闪锌矿GaN薄膜：将温度控制在1050℃，100mbar下进一步合并生长GaN薄膜，通入NH3和TMGa的流量分别10000 mol/min和26μmol/min，V/III比为300，生长时间为2h。4) Growth of sphalerite GaN film: control the temperature at 1050°C and further grow the GaN film at 100mbar . The time is 2h.
对实施例1生长在金刚石上的闪锌矿GaN薄膜样品分别进行了表面形貌和结构分析。图2是样品表面形貌及平整度的原子力显微像（AFM），从图可以看出原子级台阶层流，反应出表面很平整，均方根粗糙度(RMS)测量值仅为 0.31nm。图3是样品X射线衍射仪分析图谱（XRD），从图可以看出，样品取向性好，主要以垂直于闪锌矿（200）面的方向生长，其（200）面最高半峰宽很窄，表明闪锌矿GaN薄膜晶体质量很高。The surface morphology and structure of the sphalerite GaN film sample grown on diamond in Example 1 were analyzed respectively. Figure 2 is the atomic force microscope (AFM) image of the surface morphology and flatness of the sample. It can be seen from the figure that the atomic-level step laminar flow reflects that the surface is very flat, and the root mean square roughness (RMS) measured value is only 0.31nm . Figure 3 is the X-ray diffractometer analysis pattern (XRD) of the sample. It can be seen from the figure that the sample has good orientation and mainly grows in the direction perpendicular to the (200) plane of sphalerite, and the highest half-peak width of the (200) plane is very large. Narrow, indicating that the crystal quality of zinc blende GaN thin film is very high.
实施例2：一种在金刚石衬底上制备闪锌矿GaN薄膜的方法，具体步骤如下：Embodiment 2: a kind of method for preparing sphalerite GaN film on diamond substrate, concrete steps are as follows:
1）氟化处理金刚石衬底：对金刚石衬底进行氟化处理，氟化处理的压力设置为100mbar，功率为300mW，用XeF2等离子体处理250s。1) Fluorination treatment of diamond substrate: Fluorination treatment is performed on the diamond substrate, the pressure of fluorination treatment is set to 100mbar, the power is 300mW, and XeF 2 plasma is used for 250s.
2）生长GaN形核层：将金刚石衬底放入MOCVD反应室中，在1200℃的温度，200 mbar压力下，H2气氛中进行清洗步骤15 min。清洗步骤之后，降温至650℃， 600 mbar压力下在金刚石衬底表面生长GaN形核层，通入NH3和TMGa的流量分别为26600 μmol/min， 36μmol/min， V/III比为800，生长时间为300s。2) Growth of GaN nucleation layer: Put the diamond substrate into the MOCVD reaction chamber, and perform the cleaning step for 15 min at a temperature of 1200 ° C, a pressure of 200 mbar, and an H 2 atmosphere. After the cleaning step, the temperature was lowered to 650 ° C, and a GaN nucleation layer was grown on the surface of the diamond substrate under a pressure of 600 mbar. The flow rates of NH 3 and TMGa were 26600 μmol/min and 36 μmol/min, respectively, and the V/III ratio was 800. The growth time is 300s.
3）退火处理：升温至1200℃， 450 mbar下对GaN形核层进行高温退火6 min，退火时通入的NH3流量为630000 μmol/min。3) Annealing treatment: heat up to 1200°C, and perform high-temperature annealing on the GaN nucleation layer at 450 mbar for 6 minutes, and the flow rate of NH 3 introduced during annealing is 630,000 μmol/min.
4) 生长闪锌矿GaN薄膜：将温度控制在1150℃，150mbar下进一步合并生长GaN薄膜，通入NH3和TMGa的流量分别为20000 μmol/min和30 μmol/min，V/III比为800，生长时间为2.5h。4) Growth of sphalerite GaN film: control the temperature at 1150°C and further grow the GaN film at 150mbar, the flow rates of NH 3 and TMGa are 20000 μmol/min and 30 μmol/min respectively, and the V/III ratio is 800 , the growth time is 2.5h.
实施例3：一种在金刚石衬底上制备闪锌矿GaN薄膜的方法，具体步骤如下：Embodiment 3: a kind of method for preparing sphalerite GaN film on diamond substrate, concrete steps are as follows:
1）氟化处理金刚石衬底：对金刚石衬底进行氟化处理，氟化处理的压力设置为20mbar，功率为200mW，用XeF2等离子体处理200s。1) Fluorination treatment of diamond substrate: Fluorination treatment is performed on the diamond substrate, the pressure of the fluorination treatment is set to 20mbar, the power is 200mW, and XeF 2 plasma is used for 200s.
2）生长GaN形核层：将金刚石衬底放入MOCVD反应室中，在1200℃的温度，120 mbar压力下，H2气氛中进行清洗步骤13 min。清洗步骤之后，降温至550℃， 500 mbar压力下在金刚石衬底表面生长GaN形核层，通入NH3和TMGa的流量分别为23000 μmol/min和 33 μmol/min， V/III比为700，生长时间为250s。2) Growth of GaN nucleation layer: Put the diamond substrate into the MOCVD reaction chamber, and perform the cleaning step for 13 minutes at a temperature of 1200 ° C, a pressure of 120 mbar, and an H 2 atmosphere. After the cleaning step, the temperature was lowered to 550 °C, and a GaN nucleation layer was grown on the surface of the diamond substrate under a pressure of 500 mbar. The flow rates of NH 3 and TMGa were 23000 μmol/min and 33 μmol/min, respectively, and the V/III ratio was 700 , the growth time is 250s.
3）退火处理：升温至1150℃， 400 mbar下对GaN形核层进行高温退火2 min，退火时通入的NH3流量为450000 μmol/min。3) Annealing treatment: heat up to 1150°C, and perform high-temperature annealing on the GaN nucleation layer at 400 mbar for 2 minutes, and the flow rate of NH 3 introduced during annealing is 450,000 μmol/min.
4) 生长闪锌矿GaN薄膜：将温度控制在1100 ℃，130 mbar下进一步合并生长GaN薄膜，通入NH3和TMGa的流量分别15000 μmol/min和28 μmol/min，V/III比为500，生长时间为3h。4) Growth of sphalerite GaN thin film: control the temperature at 1100 °C and further grow the GaN thin film at 130 mbar. The flow rates of NH 3 and TMGa are 15000 μmol/min and 28 μmol/min respectively, and the V/III ratio is 500 , the growth time is 3h.
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