WO2019109966A1 - Électrode de génération de plasma et son procédé de fabrication - Google Patents

Électrode de génération de plasma et son procédé de fabrication Download PDF

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Publication number
WO2019109966A1
WO2019109966A1 PCT/CN2018/119490 CN2018119490W WO2019109966A1 WO 2019109966 A1 WO2019109966 A1 WO 2019109966A1 CN 2018119490 W CN2018119490 W CN 2018119490W WO 2019109966 A1 WO2019109966 A1 WO 2019109966A1
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Prior art keywords
needle
structures
substrate
plasma generator
array
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PCT/CN2018/119490
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English (en)
Chinese (zh)
Inventor
王雨化
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上海睿筑环境科技有限公司
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Publication of WO2019109966A1 publication Critical patent/WO2019109966A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32532—Electrodes
    • H01J37/32541—Shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32532—Electrodes
    • H01J37/3255—Material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32532—Electrodes
    • H01J37/32568—Relative arrangement or disposition of electrodes; moving means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems

Definitions

  • the present invention relates to the field of plasma technology, and in particular, to a plasma generator electrode and a method of fabricating the same.
  • Plasma is a kind of material existence, contains a large number of positively and negatively charged particles and has high physical and chemical activity. Therefore, it is widely used in the fields of film formation, structural etching, surface treatment, and decomposition of harmful gases.
  • Various plasma applications are essentially energy transfer.
  • Conventional plasma generation methods include high-energy rays such as X-rays, heating excitation, lasers, etc., and the safety of them is highly difficult.
  • the relatively safe and stable way is to generate plasma for gas discharge under high-strength electric field. The safety difficulty is mainly concentrated on high-voltage driving.
  • the main problem in mechanism is the controllability and low efficiency of gas discharge under normal air pressure.
  • the main problem in application is The plasma generated by the discharge is unevenly distributed, and it is easy to generate energy for the flow column, and it is difficult to maintain a sufficient charged particle density in the space outside the generator.
  • a targeted solution has been proposed.
  • a smaller electrode spacing can be used to achieve higher electric field strength under certain voltage conditions or to reduce the voltage required for loading under certain electric field strength conditions, but correspondingly, the charged particles are reduced in space.
  • the probability of collision in the whole inhibits the efficiency of the plasma generated by the discharge as a whole, or reduces the distribution interval of the plasma and restricts its application range; reducing the discharge pressure not only requires a complicated vacuum system, but also limits the application range;
  • Discharge and flow column generation introduce dielectric barrier discharge, generally only filament current is formed between parallel electrodes, and the distribution of charged particles in a large spatial range cannot be achieved.
  • the focus of this research is on the pulse excitation or high frequency high voltage power supply required.
  • the present invention proposes a plasma generator electrode and a method of fabricating the same to efficiently form a large range of high density plasma distribution under conditions of lower voltage driving.
  • a plasma generator electrode comprising:
  • An array of needle structures is formed on the substrate outside the plurality of columnar structures and at the bottom of the plurality of columnar structures, the array of needle structures comprising a plurality of needle-like structures.
  • the height of the needle-like structure is much lower than the height of the columnar structure.
  • a needle-like structure is also formed on the top and/or side walls of the plurality of columnar structures.
  • the tip end of the needle-like structure forms a heterojunction structure with the metal particles.
  • the single columnar structure has an aspect ratio of not less than 2 and a height of not less than 100 ⁇ m.
  • the spacing between adjacent columnar structures in the array of columnar structures is not less than the diameter of the columnar structures.
  • the single needle-like structure has an aspect ratio of not less than 10 and a diameter of not more than 10 microns.
  • the array of columnar structures is formed by etching the substrate.
  • the etching employs a patterned catalyst film as a catalyst.
  • the patterned catalyst film comprises an underlying film that is in contact with a substrate, the underlying film being of a noble metal for catalyzing etching of the substrate.
  • the patterned catalyst film further comprises an upper film, the upper film is located on the lower film, and the material of the upper film is iron, gold, silver, titanium, palladium, nickel Any one or combination of gallium, zinc, and alloys and/or oxides thereof for catalyzing the growth of the acicular structure.
  • the substrate is a silicon wafer.
  • the present invention also provides a method for manufacturing a plasma generator electrode, comprising the following steps:
  • S3 forming an array of needle structures on the substrate outside the plurality of columnar structures and at the bottom of the plurality of columnar structures, the array of needle structures comprising a plurality of needle-like structures.
  • step S3 the needle-like structure is also formed on the top and/or side walls of the columnar structure.
  • step S4 further comprising the step S4 of forming a metal particle-needle-like heterojunction structure at the top end of the needle-like structure.
  • the step S1 and the step S2 further comprise a step S12: depositing a catalyst film on the substrate and patterning the catalyst film.
  • the step S2 is specifically: forming the columnar structure array by catalytically etching the substrate in an etching solution by a patterned catalyst film.
  • the step S3 is specifically: catalyzing the growth of the needle-like structure with the patterned catalyst film as a catalyst to form an array of needle structures.
  • the patterned catalyst film comprises an underlying film that is in contact with a substrate, the underlying film being of a noble metal for catalyzing etching of the substrate.
  • the patterned catalyst film further comprises an upper film, the upper film is located on the lower film, and the material of the upper film is iron, gold, silver, titanium, palladium, nickel Any one or combination of gallium, zinc, and alloys and/or oxides thereof for catalyzing the growth of the acicular structure.
  • the plasma generator electrode provided by the invention fully utilizes the cross-scale cooperation of the columnar structure and the needle-like structure, wherein the geometrical tip effect of the needle-like structure (ie, the top end of the structure with high aspect ratio can generate a locally enhanced electric field)
  • the local electric field is concentrated to promote the direct conversion of the gas into the plasma state; and the side wall of the columnar structure contains a large number of surface states, which can further promote the proliferation and maintenance of the plasma in the diffusion in the space, thereby enabling realization at a lower voltage.
  • a wide range of high density plasma distributions are formed efficiently under driving conditions.
  • the columnar structure of the plasma generator electrode provided by the present invention can form a needle-like structure on the top end and/or the side wall of the columnar structure except that the needle-like structure is distributed at the bottom, and the tip effect and the surface state effect are the same.
  • a wide range of high density plasma distributions can be formed at lower drive voltages.
  • the plasma generator electrode provided by the present invention has a heterojunction structure of a metal particle-needle structure formed at the top end of the needle-like structure and the metal particle, and the heterojunction structure can provide more surface states, so that the gas molecule During the plasma formation by ionization, electrons have a greater chance of escaping from neutral gas molecules to further promote plasma generation efficiency.
  • the method for manufacturing a plasma generator electrode provided by the present invention uses a precious metal to catalyze etching a substrate to form a columnar structure and remains in the bottom of the columnar structure, and continues to be a catalyst for subsequent needle-like structure growth, achieving high efficiency, economy, and consistency. Cross-scale micromachining effect.
  • FIG. 1 is a front elevational view of a plasma generator electrode according to an embodiment of the present invention.
  • FIG. 2 is a schematic flow chart of a method for manufacturing a plasma generator electrode according to an embodiment of the present invention
  • 3A-3C are schematic structural views of devices corresponding to respective steps of a method for fabricating a plasma generator electrode according to an embodiment of the present invention.
  • the electrode structure of the plasma generator has been reported to directly introduce a micron or even nanometer-scale needle structure in order to enhance the local electric field, although the plasma generation efficiency can be improved while reducing the threshold of the required driving voltage.
  • the scope of action is very limited, relying only on the tip effect of the top of the needle-like structure; at the same time, the experimental results carried out by the applicant show that if uneven discharge occurs, for example, a flow column that produces high energy and high electron flux, a small needle The structure will be destroyed and invalidated.
  • the reported electrode structure of the plasma generator such as the direct introduction of micro-nano-scale needle-like structures, also microscopically utilizes the surface state provided by the needle-like structure, which has been shown to promote more ionization.
  • the charge energy transfer but since only the needle structure is adopted, the effective range is still limited to the surface of the needle structure, and the space for plasma diffusion and drift is not effectively maintained and promoted.
  • the needle-like structure with a diameter of several micrometers to nanometers combined with the micrometer-scale columnar structure can effectively improve the plasma by studying the mechanism of plasma generation and the experiment of generating plasma by a large number of gas discharges.
  • the micro-structure of the generator electrode has a limited range of defects in the plasma generation process, so that the enhancement effect of the plasma generation extends from the tip end of the needle-like structure to the diffusion space formed by the columnar structure.
  • the plasma generator electrode provided by the embodiment of the present invention includes a substrate 1 and a substrate 1 .
  • An array of columnar structures formed thereon and an array of needle structures; wherein the array of columnar structures comprises a plurality of columnar structures 2; the array of needle structures is specifically formed on a substrate outside the plurality of columnar structures and at the bottom of the plurality of columnar structures, the array of needle structures comprising Needle-like structure 3.
  • the plasma generator electrode provided by the invention fully utilizes the cross-scale cooperation of the columnar structure and the needle-like structure, wherein the geometrical tip effect of the needle-shaped structure (ie, the top end of the structure with high aspect ratio can generate a local enhanced electric field),
  • the concentrated local electric field promotes the direct conversion of the gas into the plasma state; while the side wall of the columnar structure contains a large number of surface states, which can further promote the proliferation and maintenance of the plasma in the diffusion in the space, thereby enabling driving at a lower voltage.
  • a large range of high-density plasma distribution is formed efficiently under conditions.
  • the height of the needle-like structure 3 is much lower than the height of the columnar structure 2, that is, the needle-like structure 3 is located at the bottom as a whole.
  • a needle-like structure is also formed on the top and/or side walls of the plurality of columnar structures 2, thereby providing a larger contact area and opportunity for plasma, which maintains and proliferates during plasma movement. Have a positive role in promoting.
  • the tip end of the acicular structure 3 forms a heterojunction structure with the metal particles, so that the surface state effect provided by the metal particles can be superimposed on the tip effect, further promoting plasma generation.
  • the substrate 1 silicon wafer is preferably a high-conductivity silicon wafer having a low resistivity in order to ensure effective transmission of the driving signal, wherein the high-conductivity silicon wafer refers to a silicon wafer having a resistivity of less than several tens of ohm.cm. .
  • the invention is not limited thereto, and other materials may be selected as the substrate.
  • the columnar structure array is formed by etching the substrate, and the single columnar structure 2 has an aspect ratio (width to depth ratio) of not less than 2 and a height of not less than 100 ⁇ m.
  • the spacing between adjacent columnar structures 2 in the array of columnar structures is not less than the diameter of the columnar structures 2 to ensure sufficient geometrical effects and provide sufficient surface states during plasma proliferation and motion.
  • the etching uses a patterned catalyst film as a catalyst.
  • the patterned catalyst film includes an underlying film that is in contact with the substrate 1 and the underlying film is made of a noble metal for catalyzing etching of the substrate to form a columnar structure.
  • the patterned catalyst film further includes an upper film, the upper film is located on the lower film, and the material of the upper film is iron, gold, silver, titanium, palladium, nickel, gallium, zinc and alloys thereof and/or Or any combination of oxides or combinations thereof for catalyzing the growth of the acicular structure.
  • the single needle-like structure 3 has an aspect ratio of not less than 10 and a diameter of not more than 10 micrometers to ensure a tip effect of the needle-like structure 3 during plasma generation.
  • the embodiment of the invention further provides a method for manufacturing a plasma generator electrode, comprising the following steps:
  • S3 forming an array of needle structures on the substrate outside the plurality of columnar structures and at the bottom of the plurality of columnar structures, the array of needle structures comprising a plurality of needle-like structures.
  • step S3 the needle-like structure is also formed on the top and/or side walls of the columnar structure.
  • step S4 further comprising the step S4 of forming a metal particle-needle-like heterojunction structure at the top end of the needle-like structure.
  • the step S1 and the step S2 further comprise a step S12: depositing a catalyst film on the substrate and patterning the catalyst film.
  • the step S2 is specifically: forming the columnar structure array by catalytically etching the substrate in an etching solution by a patterned catalyst film.
  • the step S3 is specifically: catalyzing the growth of the needle-like structure with the patterned catalyst film as a catalyst to form an array of needle structures.
  • the patterned catalyst film comprises an underlying film that is in contact with a substrate, the underlying film being of a noble metal for catalyzing etching of the substrate.
  • the patterned catalyst film further comprises an upper film, the upper film is located on the lower film, and the material of the upper film is iron, gold, silver, titanium, palladium, nickel Any one or combination of gallium, zinc, and alloys and/or oxides thereof for catalyzing the growth of the acicular structure.
  • the method for manufacturing the plasma generator electrode includes the following steps:
  • the substrate 1 is specifically a silicon wafer, preferably a high conductivity silicon wafer having a low resistivity to ensure efficient transmission of the driving signal.
  • S102 depositing a catalyst film 4 on the substrate 1 and patterning the catalyst film.
  • the device structure after the completion of the step is as shown in FIG. 3A.
  • the catalyst film 4 comprises an underlying film and an upper film, the lower film is in contact with the substrate 1 and the material is a noble metal for catalyzing the etching of the substrate 1; the upper film of the noble metal is made of iron, gold, silver or titanium. Any one or combination of palladium, nickel, gallium, zinc, and alloys and/or oxides thereof for catalyzing the growth of the acicular structure 3.
  • the method of depositing the catalyst film 4 on the surface of the substrate 1 comprises sputtering and sol coating, wherein sputtering is a certain energy particle (ion or neutral atom, molecule) bombarding the solid surface to obtain atoms or molecules near the surface of the solid.
  • sputtering is a certain energy particle (ion or neutral atom, molecule) bombarding the solid surface to obtain atoms or molecules near the surface of the solid.
  • sol coating refers to dispersing the desired catalyst material on the nanometer-sized particles in a liquid dispersant.
  • the etching solution is a standard mixed solution of hydrofluoric acid (molar concentration of 1.87 mol/L) and hydrogen peroxide (molar concentration of 8.94 mol/L), and the reaction temperature is obtained.
  • the hydrofluoric acid concentration can be increased by 2 times and the temperature of the reaction solution can be raised to 50 ° C.
  • the reaction time is set according to the etching depth (that is, the height of the columnar structure 2), the complexity of the pattern, the proportional relationship between the columnar structure 2 and the spacing between the columns, and can be adjusted according to the measurement result in the specific implementation process.
  • a magnetic material such as iron, cobalt, nickel is added over the noble metal layer in direct contact with the substrate 1, and then The addition of a magnetic field outside the etching solution causes the contact interface between the noble metal and the material of the substrate 1 to be subjected to a certain direction of pressure, which further promotes the order among individuals in the array of the columnar structures 2.
  • S104 growing a needle-like structure by using a patterned catalyst film remaining on the substrate and the bottom of the columnar structure as a catalyst to form an array of needle structures; the device structure after completion of the step is as shown in FIG. 3C.
  • the patterned catalyst film 4 will remain at the bottom of the substrate 1 and the columnar structure 2, because during the etching process, the metal material is substantially not consumed, and thus will follow the silicon.
  • the etching process of the wafer follows the sinking of the silicon wafer and eventually remains on the surface of the etched substrate 1 and on the bottom of the columnar structure 2.
  • the components contained in the patterned catalyst film 4 that promote the growth of the acicular structure 3 will catalyze under the corresponding conditions.
  • gold particles the applicant verified its catalytic characteristics as the growth of the needle-like structure 3: hydrogen as an ambient gas, the ratio of the arsenic source to the gallium source is 14.2.
  • the gas pressure is 10 mBar, and the reaction temperature is controlled at 430 ° C, and the array of the needle-like structures 3 of gallium arsenide nanowhiskers can be grown with a length between 100 nm and 500 nm and a diameter of less than 10 nm.
  • the results also show that a part of the catalyst material gold particles, if retained on the side wall surface or the upper surface of the columnar structure 2, can also catalyze the growth process of the gallium arsenide nanowhisker as the needle-like structure 3.
  • the catalyst material is a noble metal which has been at the top end of the needle-like structure 3
  • the noble metal particles which are stabilized after the growth process of the needle-like structure is completed will be finally stored at the top end of the needle-like structure 3, and the formed metal particle-needle structure combination
  • the heterogeneous structure can superimpose the surface state effect provided by the catalytic metal on the tip effect, further promoting plasma generation.
  • step S105 is optional as the preferred step of the present invention, and may be omitted in other embodiments.
  • the method for manufacturing a plasma generator electrode provided by the invention utilizes precious metal catalytic etching to form a columnar structure and remains in the bottom of the columnar structure (where the bottom refers to the base of the bottom of the columnar structure and the bottom structure of the columnar structure itself). ), as a catalyst for subsequent needle-like structure growth, achieving efficient, economical, and consistent cross-scale micromachining.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Catalysts (AREA)

Abstract

Cette invention concerne une électrode de génération de plasma et son procédé de fabrication. L'électrode comprend un substrat (1), un réseau de structures en colonne (2) et un réseau de structures en forme d'aiguille (3) formés sur le substrat (1). Le réseau de structures en forme d'aiguille (3) est formé sur le substrat (1) à l'extérieur du réseau de structures en colonne (2) et sur la partie inférieure du réseau de structures en colonne (2). La structure permet une utilisation complète de la coordination à échelle croisée des structures en colonne (2) et des structures en forme d'aiguille (3). L'effet de pointe géométrique des structures en forme d'aiguille (3) favorise la transformation directe de gaz dans un état de plasma par concentration d'un champ électrique local. Les parois latérales des structures en colonne (2) contiennent un grand nombre d'états de surface, capables de favoriser davantage la prolifération et le maintien de la diffusion de plasma dans un espace pour former efficacement une large plage de distribution de plasma haute densité dans des conditions de commande à basse tension. Le procédé de fabrication d'électrode utilise un métal noble qui, après gravure catalytique du substrat (1) pour former des structures en colonne (2), continue de faire office de catalyseur pour la croissance ultérieure des structures en forme d'aiguille (3), ce qui permet d'obtenir un rendement élevé, des économies de coût et un effet régulier de micro-fabrication à échelle croisée.
PCT/CN2018/119490 2017-12-07 2018-12-06 Électrode de génération de plasma et son procédé de fabrication WO2019109966A1 (fr)

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CN201711282245.8 2017-12-07
CN201711282245.8A CN107845559A (zh) 2017-12-07 2017-12-07 等离子体发生器电极及其制造方法

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CN107845559A (zh) * 2017-12-07 2018-03-27 上海睿筑环境科技有限公司 等离子体发生器电极及其制造方法

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