CN115369386B - 一种在微结构衬底上沉积金刚石的方法 - Google Patents

一种在微结构衬底上沉积金刚石的方法 Download PDF

Info

Publication number
CN115369386B
CN115369386B CN202210973814.8A CN202210973814A CN115369386B CN 115369386 B CN115369386 B CN 115369386B CN 202210973814 A CN202210973814 A CN 202210973814A CN 115369386 B CN115369386 B CN 115369386B
Authority
CN
China
Prior art keywords
diamond
substrate
silicon carbide
silicon
depositing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210973814.8A
Other languages
English (en)
Other versions
CN115369386A (zh
Inventor
魏俊俊
郝志恒
董春燕
杨志亮
刘金龙
陈良贤
李成明
高旭辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology Beijing USTB
Original Assignee
University of Science and Technology Beijing USTB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to CN202210973814.8A priority Critical patent/CN115369386B/zh
Publication of CN115369386A publication Critical patent/CN115369386A/zh
Application granted granted Critical
Publication of CN115369386B publication Critical patent/CN115369386B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
    • 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
    • C23C14/0635—Carbides
    • 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
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • 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
    • C23C14/58—After-treatment
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/274—Diamond only using microwave discharges
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/048—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with layers graded in composition or physical properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02387—Group 13/15 materials
    • H01L21/02389—Nitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02441—Group 14 semiconducting materials
    • H01L21/02447—Silicon carbide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02441—Group 14 semiconducting materials
    • H01L21/0245—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02527—Carbon, e.g. diamond-like carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

本发明涉及一种在微结构衬底上沉积金刚石的方法，特别是结构中包含热导率较高、凝聚系数较低的SiC，提供了一种通过调控微结构界面金刚石沉积速度而沉积出平整光滑的高质量金刚石层的方法。属于半导体技术和电子器件散热领域。本发明首先在抛光的硅衬底上镀制凝聚系数低的碳化硅薄膜；然后在碳化硅表面光刻显影实现图案化；然后通过ICP刻蚀制备微孔阵列；通过MPCVD沉积金刚石；最后对沉积的金刚石研磨抛光，使其表面平整化。该方法特别适用于集成电路、芯片等电子电器领域中对高效微通道散热的需求。

Description

一种在微结构衬底上沉积金刚石的方法
技术领域
本发明属于半导体技术和电子器件散热领域，具体涉及一种在微结构衬底上沉积金刚石的方法。
背景技术
晶体硅熔点高、硬度大，有脆性，是良好的半导体材料，可制成二极管、三极管、以及各种集成电路(如芯片、CPU等)。由于分布广、自然储量大、制备工艺简单，硅成为制造半导体产品的主要原材料，广泛应用于集成电路等低压、低频、低功率场景。然而，随着电子和光电器件的小型化、高度集成化，会在使用过程中产生大量的热量。例如硅基氮化镓器件，由于“自热效应”导致器件性能衰减甚至失效，因此有效的散热是提高器件稳定性和延长使用寿命的重要因素。
金刚石是自然界中热导率最高的材料，并且具有宽带隙、光学透明性，具有较高的的弹性模量、较低的线性热膨胀系数等优势，是一种理想的半导体材料。利用微波等离子体化学气相沉积(MPCVD)方法生长金刚石，使其沉积在不同的衬底材料上，如硅(Si)、钼(Mo)、碳化硅(SiC)等，从而使金刚石与半导体材料结合，应用于高功率器件中提高散热效率。但是，由于金刚石和衬底之间存在晶格失配和热失配，使得两者之间存在不可忽略的界面热阻，降低界面传热效率，使金刚石热导率高的优势无法充分发挥。
一般为了降低衬底与金刚石之间的界面热阻，会在界面处引入过渡层，或者对界面进行设计调控，如构建微结构界面。其中微结构界面理论上不仅可以增加接触面积，还可以通过影响声子传递促进界面处的热传递。中国专利CN110379782A提出在连接有GaN的SiC衬底上刻蚀出微孔，然后沉积金刚石，但是碳化硅和金刚石表面能差异较大，在其表面形核困难，更难以使金刚石沉积到SiC衬底的微孔中，使金刚石和衬底之间容易出现间隙，影响传热效果。
发明内容
本发明提供了一种在微结构衬底上沉积金刚石的方法。该方法在硅衬底表面沉积一层热导率较高、凝聚系数较低的碳化硅，然后刻蚀形成具有一定深宽比的微结构界面。使得微孔外表面为凝聚系数低的碳化硅材料，同时使微孔内部保持硅表面状态，利用微结构外表面和微孔内部表面材料凝聚系数的差异，使内外表面在金刚石沉积过程中形成金刚石生长速度之差。由于微孔内部含碳基团被捕获而发生非自发形核的几率远高于衬底表面，金刚石在微孔内具有更充足的形核生长时间，从而对微孔内部实现致密的填充，形成平整光滑的高质量金刚石层。本发明能够充分发挥微结构界面的优势，降低衬底与金刚石之间的热失配和界面热阻，解决半导体材料中的散热瓶颈问题。
为实现上述目的，本发明的技术方案如下：
本发明的目的是提供一种在微结构衬底上沉积金刚石的方法，包括以下步骤：
步骤1：沉积碳化硅：对硅衬底进行清洗后，在其表面沉积碳化硅，形成碳化硅层；
步骤2：形成掩膜：在步骤一制备的碳化硅层表面旋涂光刻胶，经光刻和显影后形成掩膜，所述掩膜表面具有阵列微结构；
步骤3：构建微孔：采用电感耦合等离子体(ICP)刻蚀工艺，在镀有碳化硅膜的硅衬底表面形成具有一定深宽比的微孔结构，所述微孔内部材质为硅，微孔表面材质为碳化硅；
步骤4：沉积金刚石：采用微波等离子体化学气相沉积(MPCVD)工艺，在微孔结构上沉积金刚石，使得硅衬底微孔内及硅衬底其它区域被完整金刚石层全部覆盖；
步骤5：金刚石平整化：对金刚石层表面进行研磨抛光。
进一步地，如步骤1所述，所述清洗包括：使硅衬底在丙酮中超声清洗10-20分钟，然后在酒精中超声清洗10-20分钟，超声频率30-40Hz，温度50℃，去除有机物、杂质等污染物，最后风干备用。
进一步地，如步骤1所述，采用物理气相沉积或化学气相沉积方法，在清洗后的硅衬底表面沉积碳化硅。例如使用电子束蒸发物理气相沉积方法镀制碳化硅薄膜，蒸发沉积过程中，E型枪所产生的高能电子束流将SiC靶材熔化蒸发，使其沉积到基板的Si片上形成薄膜。由于碳化硅材料本身具有低凝聚系数，在相同的沉积气氛中，碳化硅对活性基团的吸附性低于硅，因此金刚石更容易在硅表面形核生长。
进一步地，如步骤2所述，在SiC层表面旋涂光刻胶，基于掩膜板实现紫外光刻，通过显影去胶裸露出周期性图形化表面。镀膜过程中基片温度不超过100℃。
进一步地，如步骤3所述，通过ICP工艺选择性刻蚀衬底，在掩模板的遮挡下，使镀有碳化硅膜的硅衬底表面形成具有一定深宽比的微孔阵列。所述深宽比控制在1:(1～3)，即微孔高度与相邻微孔之间的直线距离比为1:(1～3)。微孔深度应大于碳化硅层厚度，使孔内裸露出硅衬底。深宽比理论上会影响金刚石的沉积速率，当深宽比较大时，沉积气氛中的活性基团难以抵达微孔底层，从而使金刚石层难以生长，容易出现金刚石填充不完整，在微孔底部出现较大的空隙。
进一步地，如步骤3所述，通过化学腐蚀法去除光刻胶掩膜板，之后清洗样品，获得微孔外表面具有SiC层的硅微孔结构，孔内外洁净无杂质。
进一步地，如步骤4所述，利用MPCVD方法在镀有碳化硅层的微结构硅衬底表面沉积一定厚度的金刚石层。基于碳化硅和硅凝聚系数的差异，使得微孔内硅表面的金刚石沉积速率高于微孔外碳化硅表面金刚石的沉积速率，从而使镀有碳化硅膜的硅衬底表面形成一层完全覆盖的金刚石，且金刚石薄膜完全填充微孔，表面平整，粗糙度低。沉积金刚石层的工艺参数为：微波功率1-3kW，沉积温度640-780℃，沉积气氛为甲烷和氢气的混合气体，控制甲烷比例在3-6％范围内，形核10-30min，随后以2-5％的甲烷比例生长金刚石层。
上述孔内外沉积速率的差异是基于材料本身性能实现的。因为碳化硅对沉积气氛中的活性基团的吸附效果低于硅的吸附效果，所以在相同的沉积条件下，活性基团更倾向于吸附在硅上，从而硅表面的金刚石沉积速率更快。
进一步地，如步骤5所述，依次使用粒径200μm、40μm、5μm的金刚石粉研磨金刚石层，抛光降低金刚石层的表面粗糙度，使其平整化。至此完成微结构衬底上高填充率高质量金刚石层的制备。
本发明的优点在于：
金刚石是自然界中热导率最高的材料，在小型高功率器件中具有极强的散热效果，是解决电子器件自热效应的关键材料。金刚石与衬底之间的界面热阻是充分发挥金刚石超高热导率的重要阻碍，本发明制备了一种具有高质量金刚石微柱填充的硅基半导体材料，用于增强半导体器件中散热能力，提高器件的稳定性和使用寿命。填充的金刚石微柱位可根据硅基半导体器件热点位置进行精确设计和控制；界面中引入的碳化硅介质层有低凝聚系数和较高的热导率，可以调控微结构界面处金刚生长速率，使金刚石能够更完整的填充到微孔中，同时降低界面处的晶格畸变，提高界面热传输效果。
本发明突出优势在于：
1、使用硅衬底制备微结构，成本更低，且金刚石形核更容易，能够低成本、高产量的制备异质结构。
2、在微孔外表面镀凝聚系数更低的碳化硅，微孔内保持硅表面，利用两者在金刚石沉积气氛中对活性基团的吸附差异，形成孔内外金刚石沉积速率之差，使微孔内部更好的被金刚石填充，实现金刚石与硅衬底之间的紧密连接和完整覆盖。
3、采用金刚石与衬底硅交替排列的方式降低晶格错排和畸变程度，大幅提高了散热效率。
4、采用微柱阵列结构，通过不连续的结构设计，缓释了由于热膨胀系数失配带来的热应力累积。
5、微结构界面由于侧向限制效应增强声子散射，促进界面处的热传递，降低界面热阻。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明在微结构衬底上沉积金刚石的示意图，其中，
图1A示出带有GaN的原始硅衬底材料；
图1B示出沉积碳化硅薄膜后的衬底示意图；
图1C示出ICP刻蚀后的结构示意图；
图1D示出沉积金刚石微柱后的结构示意图。
图2A为实施例1最终产品的金刚石膜扫描电镜(SEM)正面图，图2B为实施例1最终产品的金刚石膜SEM剖面图。
图3为对比例1最终产品的金刚石膜SEM图。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚，下面将结合附图及具体实施例进行详细描述。
图1为本发明在微结构衬底上沉积金刚石的示意图。其中，图1A示出带有GaN的原始硅衬底材料，硅衬底下方为GaN层；图1B示出沉积碳化硅薄膜后的衬底示意图，即在硅衬底表面生长有碳化硅层；图1C示出ICP刻蚀后的结构示意图，即在碳化硅表面进行刻蚀，且刻蚀深度大于碳化硅层的厚度，在其表面和内部形成微孔阵列；图1D示出沉积金刚石微柱后的结构示意图，即在镀有碳化硅膜的硅衬底表面形成一层完全覆盖的金刚石，且金刚石薄膜完全填充微孔。
实施例1
一种在微结构衬底上沉积金刚石的方法，包括以下步骤：
1)将尺寸为10×10mm、厚度1mm的硅衬底进行清洗，依次采用丙酮超声清洗20min，随后转移到酒精中超声20min，随后吹风机吹干备用；
2)在硅衬底表面沉积一层凝聚系数较低的碳化硅薄膜，利用电子束蒸发物理气相沉积设备(EP-PVD)沉积，腔室真空度为6.7×10-3Pa，电子束流强度30～60Ma，沉积厚度为200nm，沉积结束后继续保持高真空状态，待自然冷却后取出样品，在2.0×10-2Pa真空中退火处理，退火温度900℃，退火时间2h；
3)在碳化硅表面旋涂光刻胶，掩模板下紫外光曝光、显影，呈现周期性排列的光刻胶微柱；最后去除残余光刻胶得到表面沉积有掩膜的SiC层；
4)通过电感耦合等离子体干法刻蚀衬底材料。偏置功率为250W，先用CF4与O2的混合气体刻蚀碳化硅，CF4:O2比例为4：1，然后SF6和C4F8气体交替刻蚀Si衬底，形成直径为50μm，深100μm，间隔200μm的微孔阵列；
5)将镀有碳化硅薄膜的硅衬底置于微波等离子体化学气相沉积(MPCVD)设备中沉积金刚石。沉积气氛为甲烷和氢气的混合气体，腔压10000Pa，功率为2000W，以4％的甲烷浓度形核，以3％的甲烷浓度生长，形核时间20min，生长时间1.5h；
6)依次使用粒径200μm、40μm、5μm的金刚石粉研磨金刚石层，然后在30Hz的频率下抛光，进一步降低金刚石表面粗糙度，使其平整化。图2A为实施例1最终产品的金刚石膜扫描电镜(SEM)正面图，图2B为实施例1最终产品的金刚石膜SEM剖面图。图2A可以看到在硅衬底和碳化硅层表面形成一层完全覆盖的金刚石，且金刚石薄膜在微观上呈阵列排列。图2B可以看到在硅衬底和碳化硅层表面形成了微孔阵列，沉积的金刚石完全填充微孔。
实施例2
1)将尺寸为10×10mm、厚度1mm的硅衬底进行清洗，依次采用丙酮超声清洗15min，随后转移到酒精中超声15min，随后吹风机吹干备用；
2)在硅衬底表面沉积一层凝聚系数较低的碳化硅薄膜，利用电子束蒸发物理气相沉积设备(EP-PVD)沉积，腔室真空度为6.7×10-3Pa，电子束流强度30～60Ma，沉积厚度为150nm，沉积结束后继续保持高真空状态，带自然冷却后取出样品，在2.0×10-2Pa真空中退火处理，退火温度800℃，退火时间1.5h；
3)在碳化硅表面旋涂光刻胶，掩模板下紫外光曝光、显影，呈现周期性排列的光刻胶微柱；最后去除残余光刻胶得到表面沉积有掩膜的SiC层；
4)通过电感耦合等离子体干法刻蚀衬底材料。偏置功率为300W，先用CF4与O2的混合气体刻蚀碳化硅，CF4:O2比例为5：1，然后SF6和C4F8气体交替刻蚀Si衬底，形成直径为100μm，深200μm，间隔200μm的微孔阵列；
5)将镀有碳化硅薄膜的硅衬底置于微波等离子体化学气相沉积(MPCVD)设备中沉积金刚石。沉积气氛为甲烷和氢气的混合气体，腔压9000Pa，功率为1700W，以5％的甲烷浓度形核，以3％的甲烷浓度生长，形核时间10min，生长时间2h；
6)依次使用粒径200μm、40μm、5μm的金刚石粉研磨金刚石层，然后在40Hz的频率下抛光，进一步降低金刚石表面粗糙度，使其平整化。
对比例1
1)将尺寸为10×10mm、厚度1mm的碳化硅衬底进行清洗，依次采用丙酮超声清洗20min，随后转移到酒精中超声20min，随后吹风机吹干备用；
2)在碳化硅表面旋涂光刻胶，掩模板下紫外光曝光、显影，呈现周期性排列的光刻胶微柱；最后去除残余光刻胶得到表面沉积有掩膜的SiC层；
3)通过电感耦合等离子体干法刻蚀衬底材料。偏置功率为250W，先用CF4与O2的混合气体刻蚀碳化硅，CF4:O2比例为4：1，然后SF6和C4F8气体交替刻蚀Si衬底，形成直径为50μm，深100μm，间隔200μm的微孔阵列；
4)将镀有碳化硅薄膜的硅衬底置于微波等离子体化学气相沉积(MPCVD)设备中沉积金刚石。沉积气氛为甲烷和氢气的混合气体，腔压10000Pa，功率为2000W，以4％的甲烷浓度形核，以3％的甲烷浓度生长，形核时间20min，生长时间1.5h；
5)依次使用粒径200μm、40μm、5μm的金刚石粉研磨金刚石层，然后在30Hz的频率下抛光，进一步降低金刚石表面粗糙度，使其平整化。
对比例1与实施例1相比，仅将硅衬底替换为碳化硅衬底，且未进行碳化硅沉积，在具有微结构碳化硅衬底上沉积的金刚石扫描电镜图如图3所示。可以看出，在具有微孔的碳化硅衬底上，金刚石主要生长在微孔上表面，没有完全将微孔填充，金刚石生长质量差。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明所述原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (6)

1.一种在微结构衬底上沉积金刚石的方法，其特征在于，包括以下步骤：
步骤1：沉积碳化硅：对硅衬底进行清洗后，在其表面沉积碳化硅，形成碳化硅层；
步骤2：形成掩膜：在步骤一制备的碳化硅层表面旋涂光刻胶，经光刻和显影后形成掩膜，所述掩膜表面具有阵列微结构；
步骤3：构建微孔：采用ICP刻蚀工艺，在镀有碳化硅膜的硅衬底表面形成具有一定深宽比的微孔结构，所述深宽比控制在1:(1～3)，微孔深度大于碳化硅层厚度，使微孔内裸露出硅衬底，所述微孔内部材质为硅，微孔表面材质为碳化硅；
步骤4：沉积金刚石：采用MPCVD工艺，在微孔结构上沉积金刚石，使得硅衬底微孔内及硅衬底其它区域被完整金刚石层全部覆盖；
步骤5：金刚石平整化：对金刚石层表面进行研磨抛光。
2.根据权利要求1所述在微结构衬底上沉积金刚石的方法，其特征在于，如步骤1所述，所述清洗包括：使硅衬底在丙酮中超声清洗10-20分钟，然后在酒精中超声清洗10-20分钟，超声频率30-40Hz，温度50℃，最后风干备用。
3.根据权利要求1所述在微结构衬底上沉积金刚石的方法，其特征在于，如步骤1所述，使用电子束蒸发物理气相沉积方法镀制碳化硅薄膜，将单晶硅作为基片，蒸发沉积过程中，E型枪所产生的高能电子束流将SiC靶材熔化蒸发，使其沉积到基板的Si片上形成薄膜。
4.根据权利要求1所述在微结构衬底上沉积金刚石的方法，其特征在于，如步骤2所述，在SiC层表面旋涂光刻胶，基于掩膜板实现紫外光刻，通过显影去胶裸露出周期性图形化表面，镀膜过程中基片温度不超过100℃。
5.根据权利要求1所述在微结构衬底上沉积金刚石的方法，其特征在于，沉积金刚石层的工艺参数为：微波功率1-3kW，沉积温度640-780℃，沉积气氛为甲烷和氢气的混合气体，控制甲烷比例在3-6％范围内，形核10-30min，随后以2-5％的甲烷比例生长金刚石层。
6.根据权利要求1所述在微结构衬底上沉积金刚石的方法，其特征在于，如步骤5所述，依次使用粒径200μm、40μm、5μm的金刚石粉研磨金刚石层。
CN202210973814.8A 2022-08-15 2022-08-15 一种在微结构衬底上沉积金刚石的方法 Active CN115369386B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210973814.8A CN115369386B (zh) 2022-08-15 2022-08-15 一种在微结构衬底上沉积金刚石的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210973814.8A CN115369386B (zh) 2022-08-15 2022-08-15 一种在微结构衬底上沉积金刚石的方法

Publications (2)

Publication Number Publication Date
CN115369386A CN115369386A (zh) 2022-11-22
CN115369386B true CN115369386B (zh) 2023-07-25

Family

ID=84065675

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210973814.8A Active CN115369386B (zh) 2022-08-15 2022-08-15 一种在微结构衬底上沉积金刚石的方法

Country Status (1)

Country Link
CN (1) CN115369386B (zh)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107058944A (zh) * 2015-11-06 2017-08-18 Fei 公司 材料沉积的改进方法
CN206916217U (zh) * 2017-07-13 2018-01-23 南京波长光电科技股份有限公司 一种以硫系红外玻璃为基底的增透dlc膜
CN110863243A (zh) * 2019-11-27 2020-03-06 南京邮电大学 采用纳米结构制备高质量金刚石单晶的二次外延方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100678727B1 (ko) * 2005-04-13 2007-02-05 한국과학기술연구원 다공성 모재를 이용한 다이아몬드 쉘 및 그 제조방법
DE102010023952A1 (de) * 2010-06-16 2011-12-22 Universität Augsburg Verfahren zum Herstellen von Diamantschichten und mit dem Verfahren hergestellte Diamanten
US9469918B2 (en) * 2014-01-24 2016-10-18 Ii-Vi Incorporated Substrate including a diamond layer and a composite layer of diamond and silicon carbide, and, optionally, silicon
US10103057B2 (en) * 2014-11-11 2018-10-16 The Board Of Trustees Of The University Of Illinois Use of an inhibitor molecule in chemical vapor deposition to afford deposition of copper on a metal substrate with no deposition on adjacent SIO2 substrate
US20160230310A1 (en) * 2015-02-09 2016-08-11 Saeed Alhassan Alkhazraji Process of manufacturing pure porous diamond
CN106435518B (zh) * 2016-10-21 2018-07-17 中南大学 一种高比表面积硼掺杂金刚石电极及其制备方法和应用
WO2020111790A1 (ko) * 2018-11-30 2020-06-04 한국산업기술대학교산학협력단 다이아몬드 기판 제조 방법
CN111593316B (zh) * 2020-05-11 2022-06-21 南京岱蒙特科技有限公司 一种高比表面积超亲水的梯度硼掺杂金刚石电极及其制备方法和应用
CN112011784B (zh) * 2020-06-29 2022-09-20 南方科技大学 一种有序图案化多孔金刚石薄膜及其制备方法和用途
CN113151898B (zh) * 2021-02-18 2021-10-15 北京科技大学 一种嵌入式金刚石基碳化硅复合衬底的制备方法
CN113571409B (zh) * 2021-07-02 2022-04-15 北京科技大学 一种高导热金刚石增强碳化硅衬底的制备方法
CN113889411B (zh) * 2021-09-14 2023-11-14 北京科技大学 一种带金刚石微柱阵列的金刚石基GaN材料制备方法
CN114717540B (zh) * 2022-04-20 2022-11-29 广东奔朗新材料股份有限公司 一种金刚石增强碳化硅复合晶圆的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107058944A (zh) * 2015-11-06 2017-08-18 Fei 公司 材料沉积的改进方法
CN206916217U (zh) * 2017-07-13 2018-01-23 南京波长光电科技股份有限公司 一种以硫系红外玻璃为基底的增透dlc膜
CN110863243A (zh) * 2019-11-27 2020-03-06 南京邮电大学 采用纳米结构制备高质量金刚石单晶的二次外延方法

Also Published As

Publication number Publication date
CN115369386A (zh) 2022-11-22

Similar Documents

Publication Publication Date Title
CN113571409B (zh) 一种高导热金刚石增强碳化硅衬底的制备方法
CN102640307B (zh) 制造半导体基底的方法和制造发光装置的方法
CN108342716B (zh) 等离子体增强化学气相沉积制备二维材料的系统及方法
CN108206130B (zh) 生长在铝箔衬底上的氮化铟纳米柱外延片及其制备方法
CN110690105B (zh) 基于六方氮化硼和氮化铝在金刚石衬底上生长氮化镓的方法
CN109103070B (zh) 基于纳米图形硅衬底制备高质量厚膜AlN的方法
WO2011069370A1 (zh) 高Ge组分沟道材料层的形成方法
CN109637965B (zh) 一种采用双金刚石层实现GaN原始衬底转移的方法及应用
CN111809154B (zh) 一种制备高质量硅基氮化铝模板的方法
JP2017521878A (ja) 基板構造及びその形成方法、並びにこれを用いた窒化物半導体の製造方法
CN113889411B (zh) 一种带金刚石微柱阵列的金刚石基GaN材料制备方法
KR101941232B1 (ko) 반도체 제조용 부품, 복합체 코팅층을 포함하는 반도체 제조용 부품 및 그 제조방법
CN115369386B (zh) 一种在微结构衬底上沉积金刚石的方法
CN110629184A (zh) 介质衬底上直接生长二维六方氮化硼的方法
CN114892264B (zh) 氮化镓衬底、氮化镓单晶层及其制造方法
CN115377196A (zh) 一种以金刚石为衬底的外延GaN及其制备方法
JP4068817B2 (ja) ダイヤモンド膜の製造方法及びダイヤモンド膜
CN111847432B (zh) 大面积多层石墨烯及其制备方法
JP4768967B2 (ja) イオン注入用ステンシルマスク及びその作製方法
Bai et al. Si nanopillar arrays with nanocrystals produced by template-induced growth at room temperature
WO2008035468A1 (fr) FILM DE NANODIAMANT MINCE AYANT UNE CONDUCTIVITÉ DU TYPE n ET PROCÉDÉ DE FABRICATION DE CELUI-CI
US6979520B2 (en) Stencil mask for ion implantation
CN113571416B (zh) 一种金刚石基氮化镓高电子迁移率晶体管及其制备方法
JP3550665B2 (ja) 炭化珪素薄膜の製造方法
CN113564520A (zh) 一种GaAs与金刚石复合散热结构的制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant