CN108004522A - A kind of device and method of plasma enhanced atomic layer deposition carbonization nickel film - Google Patents

A kind of device and method of plasma enhanced atomic layer deposition carbonization nickel film Download PDF

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CN108004522A
CN108004522A CN201711104392.6A CN201711104392A CN108004522A CN 108004522 A CN108004522 A CN 108004522A CN 201711104392 A CN201711104392 A CN 201711104392A CN 108004522 A CN108004522 A CN 108004522A
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ald
ald valves
monomer
reaction chamber
temperature
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刘忠伟
桑利军
郭群
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Beijing Institute of Graphic Communication
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Beijing Institute of Graphic Communication
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—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
    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • C23C16/4554—Plasma being used non-continuously in between ALD reactions
    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • 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
    • C23C16/505—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 radio frequency discharges

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Abstract

The invention discloses a kind of device and method of plasma enhanced atomic layer deposition carbonization nickel film,Include carrier gas bottle,Hydrogen cylinder,AMD Ni monomer bottles,DAD Ni monomer bottles,Heating furnace,Mechanical pump and radio-frequency power supply,AMD Ni monomers bottles and DAD Ni monomer bottles are placed in heating mantle,Heating mantle inner wall is wrapped with heating tape,Reaction chamber is equipped with heating furnace,Chip bench is placed with reaction chamber,Chip bench is built-in with thermocouple,The gas outlet difference quality of connection flow controller one of the carrier gas bottle,Flow controller two,Flow controller three,The outlet of flow controller one is sequentially connected the import of ALD valves one and AMD Ni monomer bottles,The outlet of flow controller two is sequentially connected the import of ALD valves two and DAD Ni monomer bottles,The outlet of flow controller three is sequentially connected a bite of ALD valves three and triple valve.

Description

A kind of device and method of plasma enhanced atomic layer deposition carbonization nickel film
Technical field
The present invention relates to electrochemical catalysis and super capacitor technology field, more particularly to a kind of plasma enhanced atomic layer The device and method of depositing silicon nickel film.
Background technology
In recent years, transition metal（Fe, Co and Ni）Carbide is due to its high rigidity and fusing point, good warm and electrical conductivity etc. Characteristic, causes more concerns.In addition, they show excellent in electric energy storage, oxygen reduction reaction, evolving hydrogen reaction Catalytic performance.Compared with the research of cementite and cobalt carbide, be carbonized nickel（Ni3C）That studies is less, because carbonization nickel is in room temperature There is down metastable phase, more than 430 DEG C at a temperature of decompose.Carbonization nickel has two kinds of crystalline phases, hexagonal phase and rhombohedron Phase.However, Ni3C crystalline phases are similar to hcp Ni, and then hinder to Ni3The further investigation of C generations.With nano-scale carbide Experimental technique fast development, the experiment of nickel carbide and calculate research and achieve major progress recently.
Although several method is used previously, including vapour deposition, mechanical alloying and wet chemistry synthesis technology are come Prepare Ni3C nano particle, still, relatively thin Ni3C thin film studies it is relatively fewer.Atomic layer deposition is a kind of relatively new The technology of depositing homogeneous nano structure membrane.Compared with conventional CVD techniques, ALD can deposit tool in complicated three-dimensional substrates There is the film of good step coverage, and film thickness can be controlled exactly.In the past few decades, ALD technique has been It is successfully used to deposit hundreds of compounds, mainly inorganic material.For the nickel film that is carbonized, so far, only 250 DEG C within the temperature range of 300 DEG C, using nickel acetylacetonate as nickel precursor, pass through the report of hot ALD manufacture carbonization nickel films Road.
Plasma enhanced atomic layer deposition（PEALD）It is a kind of energy enhanced ALD methods, wherein energy of plasma It is mainly used for generating active specy（Including electronics, ion, photon, free radical and excited state species）, and then cause to chemically react. Compared with the hot ALD of tradition, PEALD reduces depositing temperature, and presoma range of choice is wide, good film composition control and higher Growth rate.Therefore, the present invention uses PEALD technologies, utilizes the carbonization nickel film under different nickel presoma progress low temperature Deposition, is applied in super capacitor and electrochemical catalysis.
The content of the invention
A kind of the defects of the object of the invention is exactly to make up prior art, there is provided plasma enhanced atomic layer deposition carbon Change the device and method of nickel film.
The present invention is achieved by the following technical solutions：
A kind of equipment of plasma enhanced atomic layer deposition carbonization nickel film, includes carrier gas bottle, hydrogen cylinder, AMD-Ni monomers Bottle, DAD-Ni monomers bottle, heating furnace, mechanical pump and radio-frequency power supply, heating is placed on by AMD-Ni monomers bottle and DAD-Ni monomer bottles In set, heating mantle inner wall is wrapped with heating tape, in heating furnace equipped with reaction chamber, is placed with chip bench in reaction chamber, built in chip bench There are thermocouple, gas outlet difference quality of connection flow controller one, flow controller two, the flow controller of the carrier gas bottle Three, the outlet of flow controller one is sequentially connected the import of ALD valves one and AMD-Ni monomer bottles, the outlet of flow controller two according to Secondary connection ALD valves two and the import of DAD-Ni monomer bottles, the outlet of flow controller three are sequentially connected ALD valves three and triple valve Flatly, the outlet of AMD-Ni monomers bottle is connected by ALD valves four with the import of reaction chamber, and the outlet of DAD-Ni monomer bottles passes through ALD valves five are connected with the import of reaction chamber, and two mouthfuls of triple valve are connected with the import of reaction chamber, the outlet of the hydrogen cylinder according to Secondary to be connected by mass flow controller four, three mouthfuls of ALD valves six and triple valve, the radio-frequency power supply passes through electromagnetic relay It is connected with reaction chamber, the outlet of reaction chamber is connected by ALD valves seven with mechanical pump.
A kind of method of plasma enhanced atomic layer deposition carbonization nickel film, comprises the following steps：
（1）AMD-Ni and DAD-Ni nickel presoma is loaded into AMD-Ni monomers bottle and DAD- in the glove box of carrier gas atmosphere respectively In Ni monomer bottles and in the heating mantle, set the temperature of heating mantle and heating tape as 95 degree, successively opening ALD valves four or ALD valves five and ALD valves seven, are evacuated to low pressure by reaction chamber and transfer pipeline, the outlet hand-operated valve of monomer bottle are opened, by AMD-Ni Low pressure is evacuated in monomer bottle or DAD-Ni monomer bottles, afterwards closes the ALD valves of above-mentioned opening and hand-operated valve, when heating mantle is with adding The torrid zone is to after design temperature, having a certain amount of nickel monomer vapours in monomer bottle, the monomer temperature of DAD-Ni is 95 DEG C, AMD-Ni Monomer temperature be 75 DEG C, be raised to the preheating for carrying out 1h after design temperature before entry into the trial, activated monomer simultaneously ensures to test During monomer vapours stablize be passed through；
（2）Deposition substrate is placed on the chip bench in reaction chamber, insertion thermocouple is heated inside chip bench, there is provided main Reaction temperature, after chip bench is raised to 95 degrees Celsius of the temperature of setting, the substrate on chip bench is pre- before entry into the trial Heat 0.5 h, to ensure that temperature is uniform in reaction process, furnace setpoint temperatures maintain the room temperature of reaction chamber, design temperature Less than 20 DEG C of chip bench temperature, in room temperature to 300 DEG C, temperature is raised to design temperature and preheats 0.5 before the deposition temperature range H ensures the constant temperature of reaction chamber；
（3）It is 10-150sccm to set mass flow controller one and two, and setting mass flow controller four is 10-300sccm, Followed by ALD single loops, comprise the following steps that：
1）ALD valves two, ALD valves five, ALD valves seven are opened successively or open ALD valves one, ALD valves four, ALD valves seven, carrier gas successively The gas feeding pipe for going deep into body bottom by monomer bottle enters, and carries DAD-Ni monomers or AMD-Ni monomers by going out at the top of opposite side Gas port enters reaction chamber, duration of ventilation 0.5s-30s through ALD valves five or ALD valves four, then the ALD valves of opening are closed；
2）Triple valve, ALD valves six and ALD valves seven are opened successively, hydrogen is passed through and blows away nickel presoma unnecessary in reaction chamber, are prevented Chemical gaseous phase deposition, duration of ventilation 1-60s only occurs；
3）Open triple valve, ALD valves six and ALD valves seven successively, at the same by electromagnetic relay control point start radio-frequency power supply into Row hydrogen gas plasma discharges, and radio-frequency power supply output power is 40-300W, discharge time 0.5-30s, by radio frequency by hydrogen Crack out hydrogen atom and participate in the reaction of substrate chemisorbed species, obtain carbonization nickel film；
4）Triple valve, ALD valves six and ALD valves seven are opened successively, hydrogen 1-60s is passed through, the accessory substance reflected is blown away, and are prevented Only impurity is incorporated into carbonization nickel film；
（4）After deposition, cool down under conditions of 50 sccm hydrogen intakes, treat that temperature is cooled to room temperature, by substrate Take out.
Step（2）Described in deposition substrate include monocrystalline silicon, silica, sheet glass, quartz plate, carbon fiber pipe, each Family macromolecule film, needs to carry out cleaning treatment, all kinds of substrates to precipitation substrate before precipitation substrate is put on chip bench Successively in acetone, isopropanol, alcohol, deionized water difference 10 min of ultrasound, chip bench is placed directly within after finally being dried up with carrier gas On.
The reaction chamber uses tubular type and disc type, and for tubular type using medium tube as settling chamber, sparking electrode is coated on medium tube Outside.
The carrier gas is nitrogen or argon gas or helium.
Nickel presoma monomer bottle constant temperature is kept using heating unit, the input quantity of nickel presoma can be lifted and avoid inputting The fluctuation of amount.At a certain temperature, nickel precursor vapor is by carrier gas（Nitrogen, argon gas or helium）Pass through mass flow controller Reaction chamber is passed through with certain flow.
Plasma discharge gas uses hydrogen.
Plasma source can use the various power supplys such as intermediate frequency, high frequency.After plasma is excited, the high energy in system Electronics and the active hydrogen substance of reducing agent molecular collision generation are lived with nickel forerunner precursor reactant generation nickle atom and CHx materials, nickel cluster Property is very high, so that at a lower temperature with hydrocarbon reaction, ultimately generates carbonization nickel.
Settling chamber can use tubular type and disc type.Tubular type settling chamber is with medium tube（Such as quartz ampoule, alundum tube）For deposition Room, sparking electrode cladding with medium tube outside.Since the shape of medium tube is different, and can be divided into straight and T-shaped.
On the other hand, nickel presoma of the present invention includes following two presomas（Corresponding film for DAD-Ni with AMD-Ni）And nickel acetylacetonate can be extended to, and cyclopentadiene nickel, other nickel presomas such as amino nickel,
Above nickel precursor can be carried along into deposition chambers with carrier gas.
Radio-frequency power supply provides continuous radio frequency input, and input power is between 40-300 W.The input of radio frequency is mainly used for Cracking hydrogen molecule becomes hydrogen atom, and when radio frequency inputs, the air-flow in hydrogen and nickel presoma carrier gas input reaction chamber should reach Stablize.
The setting of circulation can ensure the limitation saturation Chemisorption certainly of ALD reaction process, to realize atomic layer deposition Product.Air inlet and the outlet hand-operated valve of nickel presoma are opened, and opens nickel presoma this mass flow controller all the way, flow number Value is passed through high pure nitrogen as nickel presoma carrier gas, nickel precursor vapor is carried along into reaction between 10 ~ 150 sccm Chamber.Hydrogen quality flow controller is opened, flow number is passed through high-purity hydrogen between 10 ~ 300 sccm.Open radio frequency electrical Source, sets deposition power, and the 16 control points control radio frequency on LabView softwares is coupled with impulse form by quartz reaction chamber Surface reaction is carried out into corresponding RF energy, completes ALD single loops.
It is an advantage of the invention that：
1st, the depositing device that the present invention designs is simple in structure, and radio frequency input mode is convenient, and cost is low；
2nd, the depositing operation that the present invention designs can prepare continuous carbonization fine and close, conformal, purity is high at a lower temperature Nickel film.
Brief description of the drawings
Fig. 1 be DAD-Ni and AMD-Ni at 95 DEG C, hydrogen plasma atomic layer deposition is in 10:Deposition knot in 1 groove Fruit SEM schemes.
Fig. 2 be DAD-Ni 75 DEG C, 95 DEG C, 115 DEG C and AMD-Ni at 75 DEG C, 95 DEG C, 150 DEG C hydrogen etc. from Daughter atom layer is deposited schemes with the SEM in silicon base.
Fig. 3 is DAD-Ni in 75 DEG C, 95 DEG C, 115 DEG C and AMD-Ni hydrogen etc. at 75 DEG C, 95 DEG C, 150 DEG C Plasma-atomic layer is deposited schemes with the AFM in silicon base.
Fig. 4 is that the TEM of DAD-Ni and AMD-Ni carbonizations nickel film under 95 DEG C of depositing temperatures schemes.
Fig. 5 is the structure diagram of the present invention.
Embodiment
As shown in figure 5, a kind of equipment of plasma enhanced atomic layer deposition carbonization nickel film, includes carrier gas bottle 1, hydrogen Gas cylinder 2, AMD-Ni monomers bottle 3, DAD-Ni monomers bottle 4, heating furnace 5, mechanical pump 6 and radio-frequency power supply 7, by AMD-Ni monomers bottle 3 It is placed on DAD-Ni monomers bottle 4 in heating mantle 8,8 inner wall of heating mantle is wrapped with heating tape 9, and reaction chamber 10 is equipped with heating furnace 5, Chip bench is placed with reaction chamber 10, chip bench is built-in with thermocouple, the gas outlet difference quality of connection flow of the carrier gas bottle 1 Controller 1, flow controller 2 12, flow controller 3 13, the outlet of flow controller 1 are sequentially connected ALD valves one The import of 14 and AMD-Ni monomers bottle 3, the outlet of flow controller 2 12 are sequentially connected ALD valves 2 15 and DAD-Ni monomers bottle 4 Import, the outlet of flow controller 3 13 be sequentially connected a bite of ALD valves 3 16 and triple valve 17, AMD-Ni monomers bottle 3 Outlet is connected by ALD valves 4 18 with the import of reaction chamber 10, and the outlet of DAD-Ni monomers bottle 4 passes through ALD valves 5 19 and reaction The import connection of chamber 10, two mouthfuls of triple valve 17 are connected with the import of reaction chamber 10, and the outlet of the hydrogen cylinder 2 passes sequentially through Mass flow controller 4 20, three mouthfuls of ALD valves 6 21 and triple valve 17 be connected, the radio-frequency power supply 7 passes through electromagnetism relay Device 22 is connected with reaction chamber 10, and the outlet of reaction chamber 10 is connected by ALD valves 7 23 with mechanical pump 6.
A kind of method of plasma enhanced atomic layer deposition carbonization nickel film, comprises the following steps：
（1）AMD-Ni and DAD-Ni nickel presoma is loaded to 3 He of AMD-Ni monomers bottle in the glove box of carrier gas atmosphere respectively In DAD-Ni monomers bottle 4 and in heating mantle 8, the temperature of heating mantle 8 and heating tape 9 is set as 95 degree, opens ALD successively Valve 4 18 or ALD valves 5 19 and ALD valves 7 23, are evacuated to low pressure by reaction chamber 10 and transfer pipeline, open the outlet of monomer bottle Hand-operated valve, will be evacuated to low pressure, afterwards by the ALD valves and hand-operated valve of above-mentioned opening in AMD-Ni monomers bottle 3 or DAD-Ni monomers bottle 4 Close, after heating mantle 8 and heating tape 9 are to design temperature, there is a certain amount of nickel monomer vapours, the list of DAD-Ni in monomer bottle Temperature is 95 DEG C, and the monomer temperature of AMD-Ni is 75 DEG C, is raised to the preheating for carrying out 1h after design temperature before entry into the trial, Activated monomer simultaneously ensures that monomer vapours stabilization is passed through in experimentation；
（2）Deposition substrate is placed on the chip bench in reaction chamber, insertion thermocouple is heated inside chip bench, there is provided main Reaction temperature, after chip bench is raised to 95 degrees Celsius of the temperature of setting, the substrate on chip bench is pre- before entry into the trial 0.5 h of heat, to ensure that temperature is uniform in reaction process, furnace setpoint temperatures maintain the room temperature of reaction chamber 10, setting temperature Degree is less than 20 DEG C of chip bench temperature, and in room temperature to 300 DEG C, temperature is raised to design temperature and preheats before the deposition temperature range 0.5 h ensures the constant temperature of reaction chamber；
（3）It is 10-150sccm to set mass flow controller one 11 and 2 12, and setting mass flow controller four is 10- 300sccm, followed by ALD single loops, comprises the following steps that：
1）Open successively ALD valves 2 15, ALD valves 5 19, ALD valves 7 23 or open successively ALD valves 1, ALD valves 4 18, ALD valves 7 23, the gas feeding pipe that body bottom is goed deep into carrier gas by monomer bottle enter, and carry DAD-Ni monomers or AMD-Ni monomers Enter reaction chamber through ALD valves five or ALD valves four by gas outlet at the top of opposite side, duration of ventilation 0.5s-30s, then by opening ALD valves are closed；
2）Triple valve 17, ALD valves 6 21 and ALD valves 7 23 are opened successively, are passed through hydrogen by nickel presoma unnecessary in reaction chamber Blow away, prevent chemical gaseous phase deposition, duration of ventilation 1-60s；
3）Triple valve 17, ALD valves 6 21 and ALD valves 7 23 are opened successively, while are started by 22 control point of electromagnetic relay and penetrated Frequency power carries out hydrogen gas plasma electric discharge, and radio-frequency power supply output power is 40-300W, discharge time 0.5-30s, by penetrating Hydrogen is cracked out hydrogen atom and participates in the reaction of substrate chemisorbed species by frequency, obtains carbonization nickel film；
4）Triple valve 17, ALD valves 6 21 and ALD valves 7 23 are opened successively, are passed through hydrogen 1-60s, the accessory substance that will be reflected Blow away, prevent impurity to be incorporated into carbonization nickel film；
（4）After deposition, cool down under conditions of 50 sccm hydrogen intakes, treat that temperature is cooled to room temperature, by substrate Take out.
Step（2）Described in deposition substrate include monocrystalline silicon, silica, sheet glass, quartz plate, carbon fiber pipe, each Family macromolecule film, needs to carry out cleaning treatment, all kinds of substrates to precipitation substrate before precipitation substrate is put on chip bench Successively in acetone, isopropanol, alcohol, deionized water difference 10 min of ultrasound, chip bench is placed directly within after finally being dried up with carrier gas On.
The reaction chamber uses tubular type and disc type, and for tubular type using medium tube as settling chamber, sparking electrode is coated on medium tube Outside.
The carrier gas is nitrogen or argon gas or helium.
More specific detail is carried out to the present invention using DAD-Ni presomas as example below.
This example is 10 in monocrystalline silicon and depth-to-width ratio using plasmaassisted atom layer deposition process:In 1 groove in substrate Carry out the deposition of carbonization nickel film.
By the DAD-Ni presomas of 5-10 g, grind into powder loads in clean monomer bottle in the glove box of nitrogen atmosphere. Monomer bottle designs for carrier gas mode, and carrier gas is entered by the gas feeding pipe for going deep into body bottom, carries DAD-Ni monomers by another Side roof part gas outlet enters reaction chamber through hand-operated valve and ALD valves.The monomer bottle for being fitted into DAD-Ni monomers is installed in heating mantle.Beat Mechanical pump is opened, 7 pneumatic operated valves is opened, background air pressure is evacuated to by reaction chamber and with the pipeline that reaction chamber directly connects, is about 2 Pa or so.After pre- pumping half an hour, 3 and 6 two ALD valves are opened, the conveyance conduit between 3 and 6 is evacuated to background air pressure, opened Hand-operated valve at monomer bottle gas outlet, background is evacuated to by the air pressure in monomer bottle.The ALD valves of above-mentioned opening and pneumatic operated valve are closed afterwards Close.Heating mantle is set as 95 DEG C, temperature is raised to after 95 DEG C, preheats 1 h, DAD-Ni monomers are activated and cause this Monomer vapours reach stable.
Silicon（100）With 10:The etching silicon base of 1 groove is respectively washed 10 in acetone, isopropanol, alcohol and deionized water Min, after being purged totally with high pure nitrogen, is directly placed on chip bench, opens 7 pneumatic operated valves, reaction chamber is evacuated to this spirit Pressure.
Chip bench set temperature is 95 DEG C, treats that temperature is raised to after setting value, preheats 0.5 h.
Since depositing temperature is relatively low, furnace temp is also set to 95 DEG C, after design temperature is raised to, preheats 0.5 h.
After treating temperature stabilization, radio-frequency power supply is opened, opens hydrogen cylinder, 1,4 and 7 three ALD valve is opened, is passed through 50 The hydrogen of sccm, after hydrogen gas pressure is stablized, radio-frequency power supply output power is 60 W, hydrogen gas plasma electric discharge is carried out, to substrate Carry out hydrogen gas plasma and pre-process 3 min.
Once circulated by LabView software sets：
（1）3,6 and 7 three ALD valves are opened, it is 5 s to be passed through the time, this is passed through step for nickel presoma；
（2）1,4 and 7 three ALD valve is opened, it is 10 s to be passed through the time, this is nickel presoma purge step, by unnecessary nickel forerunner Body is blown away, and prevents chemical vapor deposition；
（3）1,4 and 7 three ALD valve is opened, while starts radio-frequency power supply by 16 control points and carries out hydrogen gas plasma electric discharge, Discharge power is 60 W, and discharge time is 10 s, this is hydrogen discharge step, and hydrogen is cracked out hydrogen atom by radio frequency and is joined With the reaction of substrate chemisorbed species, carbonization nickel film is obtained；
（4）1,4 and 7 three ALD valve is opened, it is 10 s to be passed through the time, this is reaction purge step, and the product reflected is blown Walk, prevent in impurity incorporation carbonization nickel film；
After setting circulation step, the mass flow controller of high pure nitrogen and hydrogen is respectively set as 50 sccm, is run LabView softwares, carry out the deposition cycle of 300 cycles.
After deposition, cool down under conditions of 50 sccm hydrogen intakes, treat that temperature is cooled to room temperature, by base Take out at bottom.
Fig. 1（a）With（b）It is using DAD-Ni and AMD-Ni as presoma respectively, is deposited on 10:It is in 1 groove as a result, passing through SEM schemes, it can be seen that deposition prepares the good carbonization nickel film of continuous conformality under the conditions of this, and deposit thickness is respectively 71.4 Nm and 45.5 nm.
Fig. 2（a-c）For using DAD-Ni as presoma, depositing temperature is respectively 75 DEG C, 95 DEG C with 115 DEG C when, silicon base SEM figures on surface；Fig. 2（d-f）For using AMD-Ni as presoma, depositing temperature is respectively 75 DEG C, 95 DEG C with 150 DEG C when, SEM figures on silicon substrate surface.The rise with depositing temperature is significantly seen from figure, the particle of film becomes larger, relatively low At a temperature of the film particles that deposit it is smaller and fine and close.
Fig. 3（a-c）For using DAD-Ni as presoma, depositing temperature is respectively 75 DEG C, 95 DEG C with 115 DEG C when, silicon base AFM figures on surface；Fig. 2（d-f）For using AMD-Ni as presoma, depositing temperature is respectively 75 DEG C, 95 DEG C with 150 DEG C when, AFM figures on silicon substrate surface.The carbonization nickel that can more accurately illustrate, when depositing temperature is relatively low, to obtain by AFM figures Film is finer and close；When depositing temperature is higher, the roughness of film becomes larger.
Fig. 4（a）With（b）Two kinds of presomas of DAD-Ni and AMD-Ni deposit carbonization nickel respectively at 95 DEG C of depositing temperature The TEM figures of film, can further be proved from test result deposition gained for the nickel film that is carbonized, and using DAD-Ni before The crystallinity for driving the carbonization nickel film of body deposition is better than AMD-Ni.

Claims (5)

  1. A kind of 1. equipment of plasma enhanced atomic layer deposition carbonization nickel film, it is characterised in that：Include carrier gas bottle, hydrogen Bottle, AMD-Ni monomers bottle, DAD-Ni monomers bottle, heating furnace, mechanical pump and radio-frequency power supply, AMD-Ni monomers bottle and DAD-Ni is mono- Body bottle is placed in heating mantle, and heating mantle inner wall is wrapped with heating tape, and in heating furnace equipped with reaction chamber, substrate is placed with reaction chamber Platform, chip bench are built-in with thermocouple, gas outlet difference quality of connection flow controller one, the flow controller of the carrier gas bottle 2nd, flow controller three, the outlet of flow controller one are sequentially connected the import of ALD valves one and AMD-Ni monomer bottles, flow control The outlet of device two processed is sequentially connected the import of ALD valves two and DAD-Ni monomer bottles, the outlet of flow controller three is sequentially connected ALD A bite of valve three and triple valve, the outlet of AMD-Ni monomer bottles are connected by ALD valves four with the import of reaction chamber, DAD-Ni monomers The outlet of bottle is connected by ALD valves five with the import of reaction chamber, and two mouthfuls of triple valve are connected with the import of reaction chamber, the hydrogen The outlet of gas cylinder pass sequentially through mass flow controller four, three mouthfuls of ALD valves six and triple valve be connected, the radio-frequency power supply leads to Cross electromagnetic relay to be connected with reaction chamber, the outlet of reaction chamber is connected by ALD valves seven with mechanical pump.
  2. A kind of 2. method of plasma enhanced atomic layer deposition carbonization nickel film, it is characterised in that：Comprise the following steps：
    （1）AMD-Ni and DAD-Ni nickel presoma is loaded into AMD-Ni monomers bottle and DAD- in the glove box of carrier gas atmosphere respectively In Ni monomer bottles and in the heating mantle, set the temperature of heating mantle and heating tape as 95 degree, successively opening ALD valves four or ALD valves five and ALD valves seven, are evacuated to low pressure by reaction chamber and transfer pipeline, the outlet hand-operated valve of monomer bottle are opened, by AMD-Ni Low pressure is evacuated in monomer bottle or DAD-Ni monomer bottles, afterwards closes the ALD valves of above-mentioned opening and hand-operated valve, when heating mantle is with adding The torrid zone is to after design temperature, having a certain amount of nickel monomer vapours in monomer bottle, the monomer temperature of DAD-Ni is 95 DEG C, AMD-Ni Monomer temperature be 75 DEG C, be raised to the preheating for carrying out 1h after design temperature before entry into the trial, activated monomer simultaneously ensures to test During monomer vapours stablize be passed through；
    （2）Deposition substrate is placed on the chip bench in reaction chamber, insertion thermocouple is heated inside chip bench, there is provided main Reaction temperature, after chip bench is raised to 95 degrees Celsius of the temperature of setting, the substrate on chip bench is pre- before entry into the trial Heat 0.5 h, to ensure that temperature is uniform in reaction process, furnace setpoint temperatures maintain the room temperature of reaction chamber, design temperature Less than 20 DEG C of chip bench temperature, in room temperature to 300 DEG C, temperature is raised to design temperature and preheats 0.5 before the deposition temperature range H ensures the constant temperature of reaction chamber；
    （3）It is 10-150sccm to set mass flow controller one and two, and setting mass flow controller four is 10-300sccm, Followed by ALD single loops, comprise the following steps that：
    1）ALD valves two, ALD valves five, ALD valves seven are opened successively or open ALD valves one, ALD valves four, ALD valves seven, carrier gas successively The gas feeding pipe for going deep into body bottom by monomer bottle enters, and carries DAD-Ni monomers or AMD-Ni monomers by going out at the top of opposite side Gas port enters reaction chamber, duration of ventilation 0.5s-30s through ALD valves five or ALD valves four, then the ALD valves of opening are closed；
    2）Triple valve, ALD valves six and ALD valves seven are opened successively, hydrogen is passed through and blows away nickel presoma unnecessary in reaction chamber, are prevented Chemical gaseous phase deposition, duration of ventilation 1-60s only occurs；
    3）Open triple valve, ALD valves six and ALD valves seven successively, at the same by electromagnetic relay control point start radio-frequency power supply into Row hydrogen gas plasma discharges, and radio-frequency power supply output power is 40-300W, discharge time 0.5-30s, by radio frequency by hydrogen Crack out hydrogen atom and participate in the reaction of substrate chemisorbed species, obtain carbonization nickel film；
    4）Triple valve, ALD valves six and ALD valves seven are opened successively, hydrogen 1-60s is passed through, the accessory substance reflected is blown away, and are prevented Only impurity is incorporated into carbonization nickel film；
    （4）After deposition, cool down under conditions of 50 sccm hydrogen intakes, treat that temperature is cooled to room temperature, by substrate Take out.
  3. 3. a kind of method of plasma enhanced atomic layer deposition carbonization nickel film according to claim 2, its feature exist In：Step（2）Described in deposition substrate include monocrystalline silicon, silica, sheet glass, quartz plate, carbon fiber pipe, all kinds of high scores Sub- film, needs to carry out cleaning treatment to precipitation substrate, all kinds of substrates exist successively before precipitation substrate is put on chip bench Acetone, isopropanol, alcohol, deionized water difference 10 min of ultrasound, are placed directly within chip bench after finally being dried up with carrier gas.
  4. 4. a kind of equipment of plasma enhanced atomic layer deposition carbonization nickel film according to claim 1, its feature exist In：The reaction chamber uses tubular type and disc type, and using medium tube as settling chamber, sparking electrode is coated on outside medium tube tubular type.
  5. 5. a kind of method of plasma enhanced atomic layer deposition carbonization nickel film according to claim 2, its feature exist In：The carrier gas is nitrogen or argon gas or helium.
CN201711104392.6A 2017-11-10 2017-11-10 A kind of device and method of plasma enhanced atomic layer deposition carbonization nickel film Pending CN108004522A (en)

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CN109554684A (en) * 2018-12-12 2019-04-02 北京大学深圳研究生院 A kind of carbonization cobalt thin film and preparation method thereof
CN112626491A (en) * 2020-12-14 2021-04-09 江南大学 Nano FeCxMethod for producing a material
CN112647059A (en) * 2020-12-14 2021-04-13 江南大学 Rapid growth of Ni by utilizing atomic layer deposition technologyxMethod for forming C film
EP3964608A1 (en) * 2020-09-02 2022-03-09 Siemens Aktiengesellschaft Direct coating of a membrane with a catalyst
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109554684A (en) * 2018-12-12 2019-04-02 北京大学深圳研究生院 A kind of carbonization cobalt thin film and preparation method thereof
EP3964608A1 (en) * 2020-09-02 2022-03-09 Siemens Aktiengesellschaft Direct coating of a membrane with a catalyst
CN112626491A (en) * 2020-12-14 2021-04-09 江南大学 Nano FeCxMethod for producing a material
CN112647059A (en) * 2020-12-14 2021-04-13 江南大学 Rapid growth of Ni by utilizing atomic layer deposition technologyxMethod for forming C film
CN114892146A (en) * 2022-05-09 2022-08-12 北京印刷学院 Powder processing device of plasma enhanced atomic layer deposition fluidized bed and application

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Application publication date: 20180508