WO2020172835A1 - 一种半导体材料激光电化学背向协同微加工方法及装置 - Google Patents

一种半导体材料激光电化学背向协同微加工方法及装置 Download PDF

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WO2020172835A1
WO2020172835A1 PCT/CN2019/076416 CN2019076416W WO2020172835A1 WO 2020172835 A1 WO2020172835 A1 WO 2020172835A1 CN 2019076416 W CN2019076416 W CN 2019076416W WO 2020172835 A1 WO2020172835 A1 WO 2020172835A1
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laser
semiconductor material
electrochemical
electrolyte
cathode
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PCT/CN2019/076416
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English (en)
French (fr)
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朱浩
朱帅杰
张朝阳
徐坤
王安斌
赵斗艳
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江苏大学
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Priority to US17/257,328 priority Critical patent/US11295953B2/en
Publication of WO2020172835A1 publication Critical patent/WO2020172835A1/zh

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    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/26—Bombardment with radiation
    • H01L21/263—Bombardment with radiation with high-energy radiation
    • H01L21/268—Bombardment with radiation with high-energy radiation using electromagnetic radiation, e.g. laser radiation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/12—Etching of semiconducting materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
    • 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
    • C23C14/08—Oxides
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material

Definitions

  • the invention relates to a processing method and device for processing structures such as micro slits, holes, grooves, etc. in the field of special processing, and in particular to a method and device for laser-electrochemical back-coordinated micro-processing of semiconductor materials.
  • Semiconductor materials represented by silicon and germanium have good structural and functional properties, and are widely used in the fields of chips, photovoltaics, medical devices, and micro-electromechanical systems.
  • the processing of microstructures with specific morphologies on the surface of semiconductor materials can achieve a variety of functions, such as: submicron-scale periodic microgrooves can enhance the anti-reflective performance of the material surface; honeycomb-like densely distributed smooth micro-pits can form micro-concave lenses Array;
  • the regular microstructure on the surface helps to change the hydrophilic properties of the material and achieve super-hydrophilic and super-hydrophobic functions.
  • the single step feed volume needs to be controlled below 250nm, resulting in low material removal efficiency; electrochemical dissolution
  • the method is limited by the characteristics of semiconductor materials, and the current density is often lower than that of metal materials, resulting in lower processing efficiency; traditional laser processing of semiconductor materials is always accompanied by more obvious thermal damage, and the advanced ultrafast represented by femtosecond lasers Laser also has disadvantages such as low removal efficiency and expensive equipment.
  • US Patent Publication No. US2017/0120345A1 discloses a method and device for laser-enhanced diamond drilling.
  • the method embeds diamond and other materials with high hardness and good light permeability in the shaft center of the metal drill bit.
  • the transmitted laser can heat and soften the material near the contact area of the drill bit, thereby improving drilling efficiency and reducing tool wear.
  • the structure of the embedded diamond material in the drill bit makes the production more complicated, and it is difficult to further reduce the diameter of the drill bit, which may limit the application of this method in the field of micro-processing.
  • the Chinese patent with publication number CN106735866A discloses a device and method for processing semiconductor materials with back-facing multi-focus laser and electrochemical composite.
  • the method uses the tool electrode as the cathode and the semiconductor sample as the anode. By controlling the potential between the two electrodes, EDM under high potential conditions and electrochemical ablation under low potential conditions can be realized.
  • the laser beam acts on the back of the semiconductor sample from bottom to top to promote the electrochemical reaction. This method can improve the etching efficiency and the surface quality of the through hole, but the laser beam and the electrode must be accurately “calibrated” to achieve compound processing, which requires high device accuracy.
  • the Chinese patent with publication number CN1919514A discloses a coaxial composite processing method of jet liquid beam and laser.
  • a high-speed jet liquid beam coaxial with the laser beam is introduced to electrolytically remove materials, eliminating recast layers and micro Cracks and residual stress.
  • This method uses metal materials as the processing object, and does not involve related properties of semiconductor materials.
  • the beam quality of the laser beam is reduced during the coaxial transmission process in the jet, making it difficult to further reduce the processing size.
  • the Chinese patent with publication number CN108526627A discloses a laser electrolytic composite processing method for semiconductor materials.
  • This method uses the characteristic that the conductivity of semiconductor materials such as monocrystalline silicon increases sharply with the increase of temperature.
  • the electrolyte jet is used near the laser processing area. Introduce an external electric field in the form of, to realize the composite processing of laser etching and electrochemical anode dissolution on the surface of the material to improve the quality of microstructure processing.
  • laser etching and electrochemical dissolution of the material occur on the same side of the material, and the incident laser beam energy will be affected by the electrolyte flow.
  • the possibility of localized processing on the back of the material is not discussed, and the technical applicability needs to be further Extension.
  • the invention is based on the characteristic that the conductivity of semiconductor materials such as silicon increases with the increase in temperature, by using short pulse laser irradiation to induce a local conductivity enhancement area near the processing area, forming an instantaneous localized conductive channel through which current preferentially passes;
  • electrochemical processing is introduced on the back of the material, and the location where the conductivity is localized can achieve high-efficiency electrochemical anodic dissolution, and the laser thermal effect on the upper surface of the material and the electrochemical anodic dissolution on the back of the material can be continuously processed to obtain a semiconductor material.
  • the micro-machining method of precise symmetrical processing has high processing efficiency, small thermal damage, and good surface quality.
  • a special processing device for this method is provided.
  • a laser-electrochemical back-coordinated micromachining method for semiconductor materials The laser is irradiated on the semiconductor material to form a local high-temperature area in the semiconductor material, and the conductivity is enhanced in a localized area.
  • the semiconductor material is connected to the anode of a DC pulse power supply;
  • the negative electrode of the pulse power supply is connected to the cathode copper plate, the cathode copper plate is placed parallel to the semiconductor material, and the gap between the two is uniform;
  • the electrolyte is introduced into the gap between the semiconductor material and the cathode copper plate in the form of a low-pressure jet through the needle to form an electrolyte layer, so that
  • the circuit between the cathode and the anode is conducted, and the electrochemical anode dissolution area on the back of the semiconductor material corresponds to the laser beam irradiation position.
  • the semiconductor material is a semiconductor material whose conductivity is positively related to temperature, preferably single crystal silicon or single crystal germanium.
  • adjusting the time and space distribution of laser energy can adjust the temperature field distribution near the laser irradiation area in the material, and then dynamically localize and control the conductivity of the material, and realize the differential control of the electrochemical anode dissolution rate of the lower surface of the semiconductor material.
  • the introduction of forced convection measures on the upper surface of the semiconductor material can effectively slow down the temperature rise outside the irradiated area, make the spatial location of the high-temperature conductive channels relatively concentrated, and improve the localization of electrochemical anode dissolution on the lower surface of the semiconductor material.
  • microstructures can be etched on the upper surface of the semiconductor material.
  • the microstructure on the upper surface corresponds to the microstructure formed by electrochemical anodic dissolution on the lower surface of the semiconductor material. .
  • the electrolyte in the metal needle is a high-concentration neutral saline solution with a mass fraction of 10%-30%, and an alkaline solution can also be used as needed, with a mass fraction of 4%-10%.
  • a semiconductor material laser electrochemical back-coordinated micromachining device including an optical path system, a stable low-pressure jet generation system, and an electrochemical machining system;
  • the optical path system includes a laser, a beam expander, a mirror, a galvanometer, and a lens;
  • the laser The emitted laser beam passes through the beam expander and is reflected by the 45° set mirror and then irradiates the semiconductor material through the galvanometer and lens;
  • the electrochemical machining system includes a DC pulse power supply, an adjustable cathode fixture, an electrolyte tank, and a current Probe and oscilloscope;
  • the stable low-pressure jet generation system is used to provide electrolyte flow, enter the metal needle to form a stable low-pressure jet, the electrolyte flow forms an electrolyte layer between the semiconductor material and the cathode copper plate, so that the circuit between the cathode and the anode is conducted.
  • the distance between the semiconductor material and the cathode copper plate can be adjusted.
  • the position of the cathode copper plate can be adjusted up and down through the two fine adjustment screws in the adjustable cathode fixture; the bottom of the adjustable cathode fixture is installed on the base, which contains spherical universal adjustment parts Realize the adjustment of the space angle between the semiconductor material and the cathode copper plate to obtain different laser incident angles and lock them by the locking device; the base is placed in the electrolyte tank; the electrolyte tank is placed on the XYZ linear motion platform, in the computer and the motion control card The position can be moved under the control of.
  • the laser is a conventional nanosecond pulse laser or a picosecond/femtosecond ultrashort pulse laser.
  • the present invention uses a focused laser beam to induce localized conductive channels in the material, and at the same time introduces electrochemical processing on the back of the semiconductor material, which corresponds to the laser irradiation
  • electrochemical processing occurs in the area of the position, and other areas are insoluble or inefficient, so as to realize the use of the upper surface of the incident laser beam to control the back electrochemical processing of the material.
  • the microstructure of the back electrochemical processing is determined by the incident laser geometry, space-time energy distribution, and scanning The path is determined, which can realize drilling, grooving, patterning processing, etc., without the use of specific cathode tools.
  • the present invention uses the temperature-sensitive characteristics of the conductivity of semiconductor materials such as single crystal silicon to convert the local high temperature area generated inside the material by laser irradiation into a high conductivity area, forming a localized conductive channel through which current preferentially passes ,
  • the current density is much higher than that of the surrounding room temperature material area, thereby limiting the electrochemical anode dissolution near the laser irradiation area, realizing the dynamic cooperative processing of the front laser thermal effect and the reverse electrochemical anode dissolution, and improving the processing localization , Improve the processing quality, while avoiding the shortcomings of strictly relying on "tool setting" steps to achieve collaborative processing.
  • the high temperature area in the material will still exist for a period of time, and the localized electrochemical machining can be continued, which improves the electrochemical dissolution efficiency.
  • the processing system of the present invention has perfect functions and is easy to assemble and realize.
  • the designed cathode and anode position and angle adjustment device has a simple structure and is easy to install and maintain.
  • Figure 1 is a schematic diagram of the system of the laser electrolysis back-coordinated micromachining method involved in the present invention
  • Figure 2 is a schematic diagram of the principle of the laser electrolysis back-coordinated micromachining method involved in the present invention
  • Figure 3 is a schematic diagram of the structure of the stable low-pressure jet generating system involved in Figure 1 of the present invention.
  • a laser-electrochemical back-to-back collaborative micromachining method for semiconductor materials uses the characteristic that the conductivity of semiconductor materials increases sharply with temperature, and generates a local temperature field by focusing the laser beam, and at the same time on the back of the material Introduce electrochemical anode dissolution to realize high-efficiency localized electrochemical processing on the back of the material, and obtain high-quality holes, grooves and other microstructures with no recast layer and no residual stress; the laser beam 2 emitted by the laser 1 irradiates the semiconductor material 9 to A localized high temperature area is formed in the material to enhance the conductivity.
  • the semiconductor material 9 is connected to the positive electrode of the DC pulse power source 20; the negative electrode of the DC pulse power source 20 is connected to the cathode copper plate 10, and the surface of the cathode copper plate 10 is flat and connected to the semiconductor material 9 is placed in parallel to make the gap uniform; the electrolyte is introduced into the gap between the anode semiconductor material 9 and the cathode copper plate 10 in the form of a low-pressure jet through the needle 8 to form an electrolyte layer 24 to make the circuit between the cathode and anode conductive, and the semiconductor material 9
  • the electrochemical anodic dissolution area on the back side corresponds to the irradiation position of the laser beam 2.
  • the semiconductor material is a semiconductor material whose electrical conductivity is positively related to temperature, including but not limited to single crystal silicon and single crystal germanium.
  • the temperature field distribution near the laser irradiation area in the material can be adjusted, and then the conductive properties of the material can be dynamically localized to control the electrochemical anode dissolution rate of the lower surface of the semiconductor material 9.
  • the temperature rise outside the irradiated area can be effectively slowed down, so that the spatial position of the high-temperature conductive channels is relatively concentrated, thereby increasing the electrical surface of the semiconductor material 9 The localization of chemical anode dissolution.
  • the space-time distribution of conductive channels in the material can be dynamically adjusted to realize different processing methods such as electrolytic drilling, slotting, and two-dimensional patterning at the bottom of semiconductor material 9.
  • the electrochemical anodic dissolution area at the bottom of the semiconductor material 9 accurately corresponds to the shape of the incident laser beam.
  • the shape of the incident beam can be adjusted by means of spectroscopy, shaping, and masking, so as to process the corresponding shape at the bottom of the semiconductor material 9, including but not limited to
  • the incident light spot is arrayed, and the micro-hole array is processed at the bottom of the semiconductor material 9 at one time; the incident beam is hollowed, and the circular ring feature is processed at the bottom of the semiconductor material 9 at one time; the incident beam is patterned at the bottom of the semiconductor material 9 at one time Process the corresponding pattern.
  • parameters such as laser beam energy, frequency, scanning speed, etc., a specific microstructure can be etched on the upper surface of the semiconductor material 9 and accurately correspond to the microstructure formed by electrochemical anodic dissolution on the lower surface of the semiconductor material 9.
  • the electrolyte in the metal needle 8 is a high-concentration neutral saline solution with a mass fraction of 10%-30%, and an alkaline solution can also be used as needed, with a mass fraction of 4%-10%.
  • a semiconductor material laser electrochemical back-to-back collaborative micromachining device includes an optical path system, a stable low-pressure jet generating system 7 and an electrochemical machining system;
  • the optical path system includes a laser 1, a beam expander 3, and a mirror 4 , Galvanometer 5 and lens 6;
  • the laser beam 2 emitted by the laser 1 passes through the beam expander 3 and is reflected by a reflector 4 set at 45°, and then irradiates the semiconductor material 9 through the galvanometer 5 and lens 6;
  • the electrochemical machining system includes a DC pulse power supply 20, an adjustable cathode fixture 12, an electrolyte tank 16, a current probe 19, and an oscilloscope 18.
  • the stable low-pressure jet generation system 7 is used to provide electrolyte flow, which enters the metal needle 8 to form a stable low pressure Jet, the electrolyte forms an electrolyte layer between the semiconductor material 9 and the cathode copper plate 10, so that the circuit between the cathode and the anode is connected.
  • hydrogen gas will be precipitated on the cathode copper plate 10, forming hydrogen bubbles 23, which are effectively removed by the impact of the low-pressure jet , To avoid the accumulation of bubbles.
  • Both the semiconductor material 9 and the cathode copper plate 10 are set on the adjustable cathode fixture 12, and the position of the cathode copper plate can be adjusted up and down through the two fine adjustment screws 11 in the adjustable cathode fixture 12.
  • the bottom of the adjustable fixture is installed on the base 13, the base 13 Contains a spherical universal adjustment component to realize the adjustment of the space angle between the semiconductor material 9 and the cathode copper plate 10 to obtain different laser incident angles, and the spherical universal adjustment component is locked by the locking device 15; the base 13 is placed in the electrolyte tank 16 In order to realize the recycling of electrolyte and prevent environmental pollution; the electrolyte tank 16 is placed on the XYZ linear motion platform 14, and the position can be moved under the control of the computer 21 and the motion control card 17.
  • the laser 1 can be either a conventional nanosecond pulse laser or a picosecond/femtosecond ultrashort pulse laser.
  • the use of ultrashort pulse laser helps to concentrate the temperature field in the material, which can further enhance the localization of electrochemical machining on the lower surface of the material and improve the processing quality.
  • the embodiment is a stable low-pressure jet generation and adjustment system, including a servo motor 32 that drives the ball screw 30 to rotate through a coupling 33, and both ends of the ball screw 30 pass through a first support seat 32 and a second support seat 35 Support;
  • the rotation of the ball screw 30 is converted into the linear motion of the piston rod 28 by the slider 29 matched with the ball screw 30, thereby pushing the electrolyte in the electrolyte 26 to be output at a constant speed.
  • the electrolyte flows into the metal needle 8 through the first one-way valve 42 and the hose 41 to form a stable low-pressure jet.
  • the angle of the low-pressure jet can be adjusted by the angle adjuster 39, and the jet impact position can be adjusted by the XYZ three-way fine-tuning platform 38.
  • the first one-way valve 25 and the second one-way valve 35 can cooperate with the ball screw 30 to move forward and backward to realize the output and suction of electrolyte.
  • the servo motor 32 drives the piston rod 28 to move forward through the ball screw 30, the first one-way valve 42 opens, the second one-way valve 35 closes, and the electrolyte enters the hose 41 under the push of the piston 27; when the servo motor 32 passes The ball screw 30 drives the piston rod 28 to move in the reverse direction, the first one-way valve 42 is closed, the second one-way valve 35 is opened, and the electrolyte in the electrolyte storage tank 36 is sucked into the electrolyte cylinder 26 through the filter 37.
  • this embodiment is a semiconductor material laser electrolysis back-coordinated micromachining method based on localized conductive channels.
  • the laser beam 2 generated by the laser 1 is adjusted and transmitted by the external optical path and then focused on the surface of the semiconductor material 9, using laser heat
  • the laser thermal effect generates a local temperature field around the irradiated area, which locally enhances the conductivity of semiconductor materials such as monocrystalline silicon.
  • a stable low-voltage electrolyte beam generator is used to introduce a low-voltage electrolyte beam on the back of the semiconductor material 9.
  • electrochemical anode dissolution is introduced locally, which can be obtained on the back of the material and the upper surface of the laser etching In addition to the corresponding microstructure, there is no thermal damage and no residual stress.
  • the electrolyte is a neutral salt solution, and alkaline solutions such as sodium hydroxide can also be used; the neutral salt solution is a neutral salt solution with appropriate concentration, with a mass fraction of 10%-30%; sodium hydroxide solution is a mass fraction of 4% -10%.
  • Embodiment 2 is a semiconductor material laser electrolysis back collaborative micromachining system based on localized conductive channels, including an optical path system, a stable low-pressure jet generating system, and an electrochemical machining system;
  • the optical path system includes a laser 1 and an external optical path, where the external
  • the optical path includes a beam expander 3, a mirror 4, a galvanometer 5 and a lens 6.
  • the laser 1 outputs the laser beam 2.
  • the beam expander 3 expands the diameter of the laser beam, adjusts the direction by the reflector 4, and controls the beam movement form by the galvanometer 5, and finally is focused by the lens 6, irradiated to the surface of the semiconductor material 9 and A localized conductive channel 22 is formed in the semiconductor material 9. Both the generation of the laser beam 2 and the movement of the galvanometer 5 are controlled by the computer 21.
  • This example also includes a stable low-pressure jet generation system 7.
  • the constant-speed electrolyte produced by the metal needle 8 forms a stable low-pressure jet, which is injected into the gap between the semiconductor material 9 and the cathode copper plate 10, and forms a thin electrolyte layer 24 .
  • This example also includes an electrolyte tank 16, which facilitates the recycling of electrolyte.
  • This example also includes an electrolytic machining system, including a DC pulse power supply 20, the negative electrode of the DC pulse power supply is connected to the cathode copper plate 9, and the DC pulse anode is connected to the semiconductor material 9, and the gap between the semiconductor material 9 and the cathode copper plate 9 is uniform.
  • a DC pulse power supply 20 the negative electrode of the DC pulse power supply is connected to the cathode copper plate 9, and the DC pulse anode is connected to the semiconductor material 9, and the gap between the semiconductor material 9 and the cathode copper plate 9 is uniform.
  • This example also includes an electrochemical machining process detection system, including a current probe 19, and the detected signal changes can be presented by an oscilloscope 18.

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Abstract

一种半导体材料激光电化学背向协同微加工装置及方法，包括光路***、稳定低压射流生成***(7)和电解加工***；光路***包括激光器(1)、扩束镜(3)、反光镜(4)、振镜(5)和透镜(6)；电解加工***包括直流脉冲电源(20)、可调阴极夹具(12)、电解液槽(16)、电流探头(19)和示波器(18)；稳定低压射流生成***(7)提供进入金属针头(8)的电解液流，电解液流在半导体材料(9)与阴极铜板(10)之间形成电解液层(24)，使阴极阳极间电路导通。以及应用装置的方法，激光辐照在半导体材料(9)上形成局域高温区域，定域增强导电性能，半导体材料(9)作为阳极；直流脉冲电源(20)的负极与阴极铜板(10)相接；电解液通过针头(8)以低压射流形式引入到半导体材料(9)与阴极铜板(10)之间间隙内，形成电解液层(24)，半导体材料(9)背面电化学阳极溶解区域对应于激光束(2)辐照位置。该装置和方法可调节阴阳极间距、与入射激光束空间角度，并利用冲液及时除去阴极析氢所产生气泡，确保实现稳定电化学阳极溶解。

Description

一种半导体材料激光电化学背向协同微加工方法及装置 技术领域
本发明涉及特种加工领域中的加工微小缝、孔、槽等结构的加工方法及装置，尤其涉及一种半导体材料激光电化学背向协同微加工方法及装置。
背景技术
以硅和锗为代表的半导体材料有着良好的结构属性与功能属性，广泛应用于芯片、光伏、医疗器械、微机电***等领域。在半导体材料表面加工出特定形貌的微细结构可以实现多种功能，例如：亚微米尺度周期性微槽结构可以增强材料表面的抗反光性能；蜂窝状紧密分布的光滑微坑群可以形成微凹透镜阵列；表面规则微结构有助于改变材料亲水性能，实现超亲水、超疏水功能。
受制于半导体材料高脆性与低断裂韧度，材料可加工性较差，微加工难度更高。得益于国内外科研机构多年探索，在对该类材料微加工方面已取得可喜进展，目前主要有微车削/铣削加工、电解加工、光刻加工、化学刻蚀加工、激光加工等。上述加工方法各有特色，有其适用场合，也有各自局限性。例如，采用微端铣方式加工单晶硅时，为确保材料去除发生在延展性区域以避免裂纹产生，需要将单步进给量控制在250nm以下，导致材料去除效率较低；采用电化学溶解方法时，受限于半导体材料特性，电流密度往往低于金属材料，导致加工效率较低；传统激光加工半导体材料始终伴随着较为明显的热损伤现象，而以飞秒激光为代表的先进超快激光又存在着去除效率低、设备昂贵等不足。
针对半导体材料微加工，国内外也提出了一些复合加工方法，将机械力、激光、电化学阳极溶解、电化学放电、化学腐蚀、水射流冲击等手段合理搭配使用，实现微加工目的。
在对现有技术进行检索后发现，公开号为US2017/0120345A1的美国专利公开了一种激光增强金刚石钻孔的方法及装置。该方法将金刚石等硬度高且透光性好的材料嵌于金属钻头轴心，加工过程中透射激光可加热软化钻头接触区域附近材料，从而提高钻孔效率、减小刀具磨损。但钻头中内嵌金刚石材料的结构使得制作较为复杂，且进一步减小钻头直径较为困难，可能会限制此方法在微细加工领域的应用。
公开号为CN106735866A的中国专利公布了一种背向多焦点激光和电化学复合加工半导体材料的装置和方法。该方法将工具电极作为阴极，半导体试样作为阳极，通过控制两电极之间的电位，可实现高电位情况下的电火花放电加工，以及低电位情况下的电化学蚀除。同时，激光束自下而上作用到半导体试样背面，促进电化学反应。此方法可提高刻蚀效率、提高通孔的表面质量，但激光束与电极要精准“对刀”实现复合加工，对装置精度要求较高。
公开号为CN1919514A的中国专利公开了一种喷射液束与激光同轴复合加工方法，在激光加工的基础上，引入与激光束同轴的高速喷射液束电解去除材料，消除再铸层、微裂纹及残余应力。该方法以金属材料为加工对象，未涉及到半导体材料相关性质。此外，限于射流直径及射流质量，激光束在射流内同轴传导过程中光束质量降低，使得进一步减小加工尺寸较为困难。
公开号为CN108526627A的中国专利公开了一种半导体材料激光电解复合加工方法，该方法利用了单晶硅等半导体材料电导率随温度升高而剧增的特性，在激光加工区域附近以电解液射流的形式引入外部电场，实现材料表面激光刻蚀与电化学阳极溶解复合加工，以提高微结构加工质量。但该方法中，激光刻蚀与材料电化学溶解发生于材料同侧，入射激光束能量会受到电解液流影响，同时，对材料背面定域加工的可能性未作探讨，技术适用性有待进一步扩展。
发明内容
本发明基于硅等半导体材料电导率随温度升高而增强的特性，通过利用短脉冲激光辐照在加工区附近诱导产生出局域电导率增强区域，形成一条电流优先通过的瞬时定域导电通道；同时，在材料背面引入电解加工，电导率定域增强的位置可实现高效电化学阳极溶解，持续实现材料上表面激光热力效应与材料背面电化学阳极溶解协同加工，从而获得一种半导体材料上下表面精确对称加工的微加工方法，加工效率高、热损伤小、表面质量好，同时提供了该方法专用的加工装置。
为了达到上述发明目的，本发明是通过如下技术方案得以实现的：
一种半导体材料激光电化学背向协同微加工方法，激光辐照在半导体材料上，在半导体材料内形成局域高温区域，定域增强导电性能，半导体材料与直流脉冲电源的正极相接；直流脉冲电源的负极与阴极铜板相接，阴极铜板与半导体材料平行放置，且两者间隙均匀；电解液通过针头以低压射流形式引入到半导体材料与阴极铜板之间间隙内，形成电解液层，使阴极与阳极间电路导通，半导体材料背面电化学阳极溶解区域对应于激光束辐照位置。
进一步的，所述半导体材料为电导率与温度正相关的半导体材料，优选单晶硅或者单晶锗。
进一步的，调节激光能量时空分布，可调节材料内激光辐照区域附近温度场分布，进而动态定域调控材料导电性能，实现半导体材料下表面电化学阳极溶解速率区别控制。
进一步的，在半导体材料上表面引入强制对流措施，可有效减缓辐照区域以外温度上升，使得高温导电通道空间位置相对集中，提高半导体材料下表面电化学阳极溶解的定域性。
进一步的，通过控制激光束能量、频率、扫描速度等参数，可在半导体材料上表面刻蚀 出相应的微结构，上表面的微结构与半导体材料下表面电化学阳极溶解形成的微结构相对应。
进一步的，通过调节入射激光束与半导体材料之间角度，可在半导体材料上下表面加工出对应的倾斜微结构。
进一步的，金属针头内的电解液为高浓度中性盐水溶液，质量分数为10％-30％，也可根据需要使用碱性溶液，质量分数为4％-10％。
一种半导体材料激光电化学背向协同微加工装置，包括光路***、稳定低压射流生成***和电解加工***；所述光路***包括激光器、扩束镜、反光镜、振镜和透镜；所述激光器发出的激光束经过扩束镜后经45°设置的反光镜反射后经过振镜和透镜辐照在半导体材料上；所述电解加工***包括直流脉冲电源、可调阴极夹具、电解液槽、电流探头和示波器；所述稳定低压射流生成***用于提供电解液流，进入金属针头形成平稳低压射流，电解液流在半导体材料与阴极铜板之间形成电解液层，使阴极阳极间电路导通。
进一步的，半导体材料与阴极铜板间距可调，通过可调阴极夹具中两个微调螺钉，可实现阴极铜板位置上下微调；可调阴极夹具底部安装于底座上，底座包含球形万向调节部件，可实现半导体材料与阴极铜板空间角度调节，获得不同的激光入射角度，并通过锁紧装置锁紧；底座放置于电解液槽中；电解液槽放置于X-Y-Z线性运动平台上，在计算机和运动控制卡的控制下可实现位置移动。
进一步的，所述激光器为常规纳秒脉冲激光器，或者皮秒/飞秒超短脉冲激光器。
有益效果：
(1)针对单晶硅等半导体材料加工工艺性较差的问题，利用单晶硅等半导体材料电导率随温度升高而增强的特性，将激光热力效应与电化学阳极溶解动态协同，实现了一种半导体材料正反面同步加工方法，正面激光蚀除效率高，背面电解加工得到的微结构无残余应力、无热损伤、表面质量好，解决了集成电路芯片封装切割、微机电***半导体微小件加工制造中大量存在的细小缝、孔、槽等结构的加工难题。
(2)本发明基于单晶硅等半导体材料电导率对温度的敏感特性，利用聚焦激光束在材料内诱导产生定域导电通道，同时在半导体材料背面引入电解加工，材料背面对应于激光辐照位置的区域发生快速电化学阳极溶解，其他区域则不溶解或效率低下，从而实现利用上表面入射激光束控制材料背面电解加工，背面电解加工的微结构由入射激光几何形状、时空能量分布、扫描路径等决定，可实现打孔、切槽、图案化加工等，无需使用特定阴极工具。
(3)本发明利用单晶硅等半导体材料电导率对温度的敏感特性，将激光辐照在材料内部产生的局域高温区域转化为高电导率区域，形成一条电流优先通过的定域导电通道，其中的电流密度远高于周围常温材料区域，从而将电化学阳极溶解限制在激光辐照区域附近，实现 了正面激光热力效应与反面电化学阳极溶解的动态协同加工，提高了加工定域性，改善加工质量，同时避免了严格依赖“对刀”步骤才能实现协同加工的不足。此外，激光脉冲间隙内，由于冷却过程中温度场变化的连续性，材料内高温区域仍会存在一段时间，定域电解加工得以延续，提高了电化学溶解效率。
(4)本发明的加工***功能完善，易于组装实现。所设计的阴阳极位置及角度调节装置结构简单，易于安装、检修。
附图说明
附图1为本发明涉及到的激光电解背向协同微加工方法的***示意图；
附图2为本发明涉及到的激光电解背向协同微加工方法的原理示意图；
附图3为本发明图1涉及到的稳定低压射流生成***结构示意图。
附图标记如下：
1、激光器，2、激光束，3、扩束镜，4、反光镜，5、振镜，6、透镜，7、稳定低压射流生成***，8、金属针头，9、半导体材料，10、阴极铜板，11、微调螺钉，12、可调阴极夹具，13、万向调节底座，14、X-Y-Z线性运动平台，15、锁紧装置，16、电解液槽，17、运动控制卡，18、示波器，19、电流探头，20、直流脉冲电解电源，21、计算机，22、瞬时定域导电通道，23、氢气气泡，24、电解液层，25、电解加工微孔；26、电解液缸，27、活塞，28、活塞杆，29、滑块，30、滚珠丝杠，31、第一支撑座，32、伺服电机，33、联轴器，34、第二支撑座，35、第二单向阀，36、电解液存储槽，37、过滤器，38、XYZ三向调节平台；39、射流角度调节器，40、可调连杆，41、软管，42、第一单向阀。
具体实施方式
为对本发明做进一步的了解，现结合附图做进一步的描述：
结合附图1和2，一种半导体材料激光电化学背向协同微加工方法，利用半导体材料电导率随温度升高而急剧增强的特性，通过聚焦激光束产生局域温度场，同时在材料背面引入电化学阳极溶解，实现材料背面高效定域电解加工，获得无再铸层、无残余应力的高质量孔、槽等微结构；激光器1发出的激光束2辐照在半导体材料9上，在材料内形成局域高温区域，定域增强导电性能，半导体材料9与直流脉冲电源20的正极相接；直流脉冲电源20的负极与阴极铜板10相接，阴极铜板10表面平坦，并与半导体材料9平行放置，使得其间间隙均匀；电解液通过针头8以低压射流形式引入到阳极半导体材料9与阴极铜板10之间间隙内，形成电解液层24，使阴阳极间电路导通，半导体材料9背面电化学阳极溶解区域对应于激光束2辐照位置。
其中，所述半导体材料为电导率与温度正相关的半导体材料，包括但不限于单晶硅与单 晶锗。
通过调节入射激光能量时空分布，可调节材料内激光辐照区域附近温度场分布，进而动态定域调控材料导电性能，实现半导体材料9下表面电化学阳极溶解速率区别控制。
通过在半导体材料9上表面引入强制对流措施，如添加流动水层、吹冷却气体等，可有效减缓辐照区域以外温度上升，使得高温导电通道空间位置相对集中，进而提高半导体材料9下表面电化学阳极溶解的定域性。
通过激光束运动路径规划、入射激光能量时空分布调控等手段，可动态调整材料内导电通道时空分布，实现半导体材料9底部电解打孔、切槽、二维图案化等不同加工方式。
半导体材料9底部电化学阳极溶解区域精确对应于入射激光束形状，可通过分光、整形、添加掩模等手段，调节入射光束形状，从而在半导体材料9底部加工出对应形状，包括但不限于使入射光斑阵列化，在半导体材料9底部一次性加工出微孔阵列；使入射光束空心化，在半导体材料9底部一次性加工出圆环特征；使入射光束图案化，在半导体材料9底部一次性加工出相应图案。可通过控制激光束能量、频率、扫描速度等参数，可在半导体材料9上表面刻蚀出特定微结构，并与半导体材料9下表面电化学阳极溶解形成的微结构精确对应。
可通过调节入射激光束2与半导体材料9之间角度，可在半导体材料9上下表面加工出精确对应的倾斜微结构。金属针头8内的电解液为高浓度中性盐水溶液，质量分数为10％-30％，也可根据需要使用碱性溶液，质量分数为4％-10％。
结合附图1，一种半导体材料激光电化学背向协同微加工装置，包括光路***、稳定低压射流生成***7和电解加工***；所述光路***包括激光器1、扩束镜3、反光镜4、振镜5和透镜6；所述激光器1发出的激光束2经过扩束镜3后经45°设置的一块反光镜4反射后经过振镜5和透镜6辐照在半导体材料9上；所述电解加工***包括直流脉冲电源20、可调阴极夹具12、电解液槽16、电流探头19和示波器18；所述稳定低压射流生成***7用于提供电解液流，进入金属针头8形成平稳低压射流，电解液在半导体材料9与阴极铜板10之间形成电解液层，使阴阳极间电路导通，电解过程中在阴极铜板10上会析出氢气，形成氢气气泡23，依靠低压射流冲击有效去除，避免气泡聚集。
半导体材料9与阴极铜板10均设置在可调阴极夹具12上，通过可调阴极夹具12中两个微调螺钉11，可实现阴极铜板位置上下微调；可调夹具底部安装于底座13上，底座13包含球形万向调节部件，用以实现半导体材料9与阴极铜板10空间角度调节，获得不同的激光入射角度，并且球形万向调节部件通过锁紧装置15锁紧；底座13放置于电解液槽16中，以实现电解液的回收利用，防止环境污染；电解液槽16放置于X-Y-Z线性运动平台14上，在计算机21和运动控制卡17的控制下可实现位置移动。
所述激光器1既可用常规纳秒脉冲激光器，也可采用皮秒/飞秒超短脉冲激光器。使用超短脉冲激光器有助于材料内温度场集中，可进一步增强材料下表面电解加工的定域性，提高加工质量。
结合附图3，实施例为稳定低压射流生成及调节***，包括伺服电机32通过联轴器33带动滚珠丝杠30转动，滚珠丝杆30两端通过第一支撑座32与第二支撑座35支撑；通过与滚珠丝杠30匹配的滑块29将滚珠丝杠30的转动转化为活塞杆28的直线运动，从而推动电解液26中的电解液以恒速输出。电解液经第一单向阀42、软管41流入金属针头8，形成稳定低压射流。低压射流角度可由角度调节器39调节，射流冲击位置可由XYZ三向微调平台38调节。第一单向阀25与第二单向阀35可配合滚珠丝杠30正反向运动实现电解液输出与吸入。当伺服电机32经滚珠丝杠30带动活塞杆28正向运动，第一单向阀42开启，第二单向阀35闭合，电解液在活塞27推动下进入软管41；当伺服电机32经滚珠丝杠30带动活塞杆28反向运动，第一单向阀42闭合，第二单向阀35开启，电解液存储槽36内的电解液经过滤器37被吸入电解液缸26中。
实施例1：
结合附图2，本实施例为基于定域导电通道的半导体材料激光电解背向协同微加工方法，将激光器1产生的激光束2经外部光路调节传输后聚焦于半导体材料9表面，利用激光热力效应进行高效材料去除，完成微孔、微槽加工。同时，激光热效应在辐照区域周边产生局域温度场，定域增强单晶硅等半导体材料的导电性能。在此基础上，利用稳定低压电解液束生成装置在半导体材料9背面引入低压电解液束，在电导率增强的区域内，定域引入电化学阳极溶解，可在材料背面获得与上表面激光蚀除相对应的微结构，且无热损伤、无残余应力。电解液为中性盐水溶液，也可使用氢氧化钠等碱性溶液；中性盐水溶液为浓度适当的中性盐水溶液，质量分数为10％-30％；氢氧化钠溶液为质量分数4％-10％。
实施例2：本实施例为基于定域导电通道的半导体材料激光电解背向协同微加工***，包括光路***、稳定低压射流生成***和电解加工***；光路***包括激光器1和外部光路，其中外部光路包括扩束镜3、反光镜4、振镜5和透镜6。激光器1输出激光束2，由扩束镜3扩大激光束直径，经反光镜4调节方向，由振镜5控制光束运动形式，最终经透镜6聚焦后，辐照到半导体材料9表面，并在半导体材料9内形成定域导电通道22。激光束2生成及振镜5的运动都由计算机21控制。
本实例还包括稳定低压射流生成***7，产生的恒速电解液经金属针头8后形成稳定低压射流，冲射到半导体材料9与阴极铜板10之间的空隙内，并形成薄电解液层24。本实例还包括电解液槽16，有利于电解液回收利用。
本实例还包括电解加工***，包括直流脉冲电源20，直流脉冲电源负极与阴极铜板9相连，直流脉冲正极与半导体材料9相连，且半导体材料9与阴极铜板9间隙均匀。金属针头8通入低压电解液束后，阴阳极导通，在激光辐照区域附近电导率增强，电流优先通过，定域提高电化学阳极溶解速率，形成材料去除，得到微孔25。
本实例还包括电解加工过程检测***，包括电流探头19，探测到的信号变化可由示波器18呈现。
所述实施例为本发明的优选的实施方式，但本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。

Claims (10)

  1. 一种半导体材料激光电化学背向协同微加工方法，其特征在于，激光辐照在半导体材料(9)上，在半导体材料(9)内形成局域高温区域，定域增强导电性能，半导体材料(9)作为阳极与直流脉冲电源(20)的正极相接；直流脉冲电源(20)的负极与阴极铜板(10)相接，阴极铜板(10)与半导体材料(9)平行放置，且两者存在一定的间隙；电解液通过针头(8)以低压射流形式引入到半导体材料(9)与阴极铜板(10)之间间隙内，形成电解液层(24)，使阴极与阳极间电路导通，半导体材料(9)背面电化学阳极溶解区域对应于激光束(2)辐照位置。
  2. 根据权利要求1所述的半导体材料激光电化学背向协同微加工方法，其特征在于，所述半导体材料(9)为电导率与温度正相关的半导体材料，可选单晶硅或者单晶锗。
  3. 根据权利要求1所述的半导体材料激光电化学背向协同微加工方法，其特征在于，通过调节激光能量时空分布，可调节材料内激光辐照区域附近温度场分布，进而动态定域调控材料导电性能，从而实现半导体材料(9)下表面电化学阳极溶解速率区别控制。
  4. 根据权利要求1所述的半导体材料激光电化学背向协同微加工方法，其特征在于，在半导体材料(9)上表面引入强制对流措施，可减缓辐照区域以外温度上升，使得高温导电通道空间位置相对集中，提高半导体材料(9)下表面电化学阳极溶解的定域性。
  5. 根据权利要求1所述的半导体材料激光电化学背向协同微加工方法，其特征在于，通过控制激光束能量、频率、扫描速度参数，可在半导体材料(9)上表面刻蚀出特定微结构，且上表面激光刻蚀所得微结构与半导体材料(9)下表面电化学阳极溶解形成的微结构相对应。
  6. 根据权利要求1所述的半导体材料激光电化学背向协同微加工方法，其特征在于，通过调节入射激光束(2)与半导体材料(9)之间角度，可在半导体材料(9)上下表面加工出对应的倾斜微结构。
  7. 根据权利要求1所述的半导体材料激光电化学背向协同微加工方法，其特征在于，金属针头(8)内的电解液为高浓度中性盐水溶液，质量分数为10％-30％，或者根据需要使用碱性溶液，质量分数为4％-10％。
  8. 一种半导体材料激光电化学背向协同微加工装置，包括光路***、稳定低压射流生成***(7)和电解加工***；其特征在于，所述光路***包括激光器(1)、扩束镜(3)、反光镜(4)、振镜(5)和透镜(6)；所述激光器(1)发出的激光束(2)经过扩束镜(3)后经45°设置的反光镜(4)反射后经过振镜(5)和透镜(6)辐照在半导体材料(9)上；所述电解加工***包括直流脉冲电源(20)、可调阴极夹具(12)、电解液槽(16)、电流探头(19)和示波器(18)；所述稳定低压射流生成***(7)用于提供电解液流，进入金属针头(8)形成平稳低压射流，电解液流在半导体材料(9)与阴极铜板(10)之间形成电解液层(24)， 使阴极阳极间电路导通。
  9. 根据权利要求8所述的半导体材料激光电化学背向协同微加工装置，其特征在于，半导体材料(9)与阴极铜板(10)均设置在可调阴极夹具(12)上，通过可调阴极夹具(12)中两个微调螺钉(11)，实现阴极铜板(10)位置上下微调；可调阴极夹具(12)底部安装于底座(13)上，底座(13)包含球形万向调节部件，用以实现半导体材料(9)与阴极铜板(10)空间角度的调节，获得不同的激光入射角度，并且球形万向调节部件通过锁紧装置(15)锁紧；底座(13)放置于电解液槽(16)中；电解液槽(16)放置于X-Y-Z线性运动平台(14)上，在计算机(21)和运动控制卡(17)的控制下可实现位置移动。
  10. 根据权利要求8所述的半导体材料激光电化学背向协同微加工装置，其特征在于，所述激光器(1)为纳秒脉冲激光器，或者皮秒/飞秒超短脉冲激光器。
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