CN111411345A - Method for preparing elemental palladium film by atomic layer deposition technology - Google Patents
Method for preparing elemental palladium film by atomic layer deposition technology Download PDFInfo
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- CN111411345A CN111411345A CN202010230844.0A CN202010230844A CN111411345A CN 111411345 A CN111411345 A CN 111411345A CN 202010230844 A CN202010230844 A CN 202010230844A CN 111411345 A CN111411345 A CN 111411345A
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- hydrazine
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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
- C23C16/44—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
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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
- C23C16/06—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 metallic material
- C23C16/18—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 metallic material from metallo-organic compounds
Abstract
The invention relates to the technical field of elemental palladium film manufacturing methods, and discloses a method for preparing an elemental palladium film by an atomic layer deposition technology, which comprises a palladium precursor and a hydrazine reductive precursor, wherein the palladium precursor can adopt palladium hexafluoroacetylacetonate Pd (hfac)2, the hydrazine reductive precursor can adopt anhydrous hydrazine, methyl hydrazine, ethyl hydrazine, propyl hydrazine, tert-butyl hydrazine and other C1-C5 hydrocarbon chain reductive precursors, and the hydrazine reducing agent has a structural formula of R1R2N-NR3R4, wherein R1, R2, R3 and R4 comprise hydrogen atoms and C1-C5 hydrocarbon chains, and R1, R2, R3 and R4 can be the same or different. The invention selects hydrazine reducing agent as reducing precursor, can directly utilize thermal atomic layer deposition technology to deposit simple substance palladium film, is superior to plasma hydrogen, oxygen, ozone and other gases adopted in the prior art, is more convenient, safer and easier to operate, can avoid the inconvenience in operation of plasma hydrogen, plasma ammonia and the like, can simplify the preparation process of simple substance palladium film, and saves cost.
Description
Technical Field
The invention relates to the technical field of elemental palladium film manufacturing methods, in particular to a method for preparing an elemental palladium film by an atomic layer deposition technology.
Background
In recent years, noble and transition metals have found widespread use in a variety of areas of high and new technology and military technology, such as microelectronics, optics, electrode materials, fuel cells, gas sensors, and aerospace, due to certain unique and superior physicochemical properties, such as high melting point, high chemical stability, high strength, good ductility, oxidation resistance, corrosion resistance, high catalytic activity, and good electrical conductivity.
The existing methods for preparing metal films generally include physical vapor deposition, electrochemical deposition, sol-gel, halide chemical vapor deposition, metal organic chemical vapor deposition and the like. Physical vapor deposition and chemical vapor deposition are the most commonly used, however, the physical vapor deposition method has high deposition temperature and poor film forming capability on the surface of a complex-shaped component, and the chemical vapor deposition method has defects in precise control of the purity and thickness of a thin film.
At present, methods for preparing a metal elemental palladium film generally include physical vapor deposition, electrochemical deposition, sol-gel, halide chemical vapor deposition, metal organic chemical vapor deposition and the like, wherein the physical vapor deposition and the chemical vapor deposition are most commonly used, however, the physical vapor deposition method has high deposition temperature and poor film forming capability on the surface of a component with a complex shape, and the chemical vapor deposition method has defects in the aspect of precise control of the purity and the thickness of the film.
Pd a L D is not insignificant and in recent years a L D processes using different precursors have been tried, Pd (keim2)2 with O2 as co-reactant leads to the formation of metallic Pd films but with poor adhesion on alumina substrates and more importantly to a self-limiting growth pulse time when adding precursors, therefore this process has not reached a L D, a L D based on Pd (thd)2 and O3 also leads to unsatisfactory results because the films are not homogeneous and partially oxidized and show significant fragments of bound precursor ligands, so far palladium hexafluoroacetylacetonate Pd (hfac)2 has been the most widely used precursor for Pd a L D at present, leading to the best results, Pd a L D processes with Pd (hfac)2 as precursor and O2 as co-reactant have been unsuccessful, when dosed with O2 or mixed with any other oxidizer, the Pd a 632D of Pd or its oxide can not achieve a as a precursor in operation, a 2D, can be deposited as a hydrogen ion in reaction with hydrogen ions, and can lead to a significant reduction of the entire active hydrogen ions deposited in H638, which, in turn leads to a high-activity reduction processes, which, in the final H638, which, and also lead to a high-H-9-H precipitation processes.
The atomic layer deposition (A L D) has low requirement on deposition temperature due to a specific self-limiting reaction mechanism, the thickness of the prepared film can be accurately controlled, and the step coverage rate is excellent.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a method for preparing an elemental palladium film by an atomic layer deposition technology, which has the advantages that: hydrazine reducing agent is selected as a reducing precursor, and the simple substance palladium film can be deposited by directly utilizing a thermal atomic layer deposition technology; the method is superior to plasma hydrogen, oxygen, ozone and other gases adopted in the prior art, is more convenient, safer and easier to operate, can avoid the inconvenience in operation of plasma hydrogen, plasma ammonia and the like, can simplify the preparation process of the simple substance palladium film, saves the cost, and solves the problem of unstable capacity of the simple substance palladium film production method in the prior art.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing an elemental palladium film by an atomic layer deposition technology comprises a palladium precursor and a hydrazine reductive precursor.
Preferably, palladium hexafluoroacetylacetonate pd (hfac)2 is used as the palladium precursor.
Preferably, the hydrazine reductive precursor can adopt anhydrous hydrazine, methyl hydrazine, ethyl hydrazine, propyl hydrazine, tert-butyl hydrazine and other C1-C5 hydrocarbon chain reductive precursors, and the hydrazine reductive precursor has a structural formula of R1R2N-NR3R4, wherein R1, R2, R3 and R4 comprise hydrogen atoms and C1-C5 hydrocarbon chains, and R1, R2, R3 and R4 can be the same or different.
Preferably, the reaction temperature of the method is 50-400 ℃, the palladium source Pd (hfac)2 is a palladium precursor, the heating temperature of the palladium source is 120 ℃, the hydrazine is a reducing source, the heating temperature is 30-70 ℃, the heating temperature of the transportation pipeline and the A L D valve is 150-200 ℃, and the precursor source is ensured to be transported in a gas phase without condensation.
A method for preparing an elemental palladium thin film by an atomic layer deposition technique, the method comprising the steps of:
s1, heating the atomic layer deposition equipment to a temperature range of 100 ℃ and 400 ℃, wherein the limit pressure after vacuumizing is 0.1-10 Pa;
s2, the atomic layer deposition system is heated uniformly with the temperature range of 100-;
s3, opening a palladium source atomic layer deposition pulse valve, wherein the opening time range of the pulse valve is 50-2000ms, so that a palladium source enters an equipment reaction chamber, and is adsorbed and reacted with the surface of a substrate;
s4, adopting inert gas as carrier gas, cleaning the palladium source which is not completely reacted and hexafluoroacetylacetone by-products generated by the reaction, wherein the cleaning time range is 1-200S;
s5, opening a hydrazine precursor atomic layer deposition pulse valve, wherein the opening time of the pulse valve is 10-500ms, so that the hydrazine precursor enters the reaction chamber, and is adsorbed and reacted with the surface of the substrate;
s6, cleaning the reductive precursor which is not completely reacted and the ammonia by-product generated by the reaction by using inert gas as carrier gas;
s7, forming a circulating simple substance palladium film;
s8, the thickness of the simple substance palladium film can be accurately controlled by controlling the circulation times.
(III) advantageous effects
The invention provides a method for preparing an elemental palladium film by an atomic layer deposition technology. The method has the following beneficial effects:
the hydrazine reducing agent is selected as a reducing precursor, and the simple substance palladium film can be deposited by directly utilizing a thermal atomic layer deposition technology, which is superior to the plasma gases such as hydrogen, oxygen, ozone and the like adopted in the prior art; in the using process, the operation is more convenient, safer and easier; the method can avoid the inconvenience in operation of plasma hydrogen, plasma ammonia and the like, simplify the preparation process of the simple substance palladium film and save the cost.
Drawings
FIG. 1 is a schematic view of an embodiment of the present invention;
FIG. 2 is a scanning electron microscope of the elemental palladium thin film of the present invention;
FIG. 3 is a schematic diagram of an EDS for depositing a palladium film on a silicon substrate according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in the figures 1-3, the invention provides a technical scheme that the method for preparing the elemental palladium thin film by the atomic layer deposition technology comprises a palladium precursor and a hydrazine reducing precursor, wherein the palladium precursor can adopt palladium hexafluoroacetylacetonate Pd (hfac)2, the hydrazine reducing precursor can adopt C1-C5 hydrocarbon chain reducing precursors such as anhydrous hydrazine, methyl hydrazine, ethyl hydrazine, propyl hydrazine, tert-butyl hydrazine and the like, and the hydrazine reducing agent has a structural formula of R1R2N-NR3R4, wherein R1, R2, R3 and R4 comprise hydrogen atoms and C1-C5 hydrocarbon chains, R1, R2, R3 and R4 can be the same or different, the reaction temperature of the method is 50-400 ℃, the palladium source Pd (hfac)2 is palladium, the heating temperature of the palladium source is 120 ℃, the hydrazine reducing source is the heating temperature of 30-70 ℃, the heating temperature of a transport pipeline and the heating temperature of an A L D valve is 150 ℃, and the heating temperature of the precursor is 200 ℃ to ensure that the precursor is not condensed in a gas phase under the atmosphere.
The first embodiment is as follows:
a method for preparing an elemental palladium film by using an atomic layer deposition technology with palladium hexafluoroacetylacetonate Pd (hfac)2 as a palladium precursor and propylhydrazine as a hydrazine reductive precursor comprises the following steps:
s1, heating the atomic layer deposition equipment to 200 ℃, wherein the limit pressure after vacuumizing is 0.1-10 Pa;
s2, heating the atomic layer deposition system uniformly with a temperature value of 200 ℃, a pressure value of 10-200Pa, a heating time of 40min, and then starting a carrier gas flow range of 10-200 sccm;
s3, opening a pulse valve for atomic layer deposition of palladium hexafluoroacetylacetonate, wherein the opening time of the pulse valve is 50-2000ms, and enabling the palladium hexafluoroacetylacetonate to enter an equipment reaction chamber to be adsorbed and react with the surface of a substrate;
s4, cleaning unreacted hexafluoroacetylacetone palladium and hexafluoroacetylacetone byproducts generated by the reaction by using inert gas as carrier gas, wherein the cleaning time range is 1-200S;
s5, opening an anhydrous hydrazine atomic layer deposition pulse valve, wherein the opening time of the pulse valve is within the range of 10-500ms, so that propylhydrazine enters a reaction chamber, and is adsorbed and reacted with the surface of the substrate;
s6, cleaning the reductive precursor which is not completely reacted and the ammonia by-product generated by the reaction by using inert gas as carrier gas;
s7, forming a circulating simple substance palladium film;
s8, the thickness of the simple substance palladium film can be accurately controlled by controlling the circulation times, 500 circulations are carried out, the thickness of the deposited simple substance palladium film is about 25.8nm, and the resistivity of the palladium film is 4.6 mu omega cm by using a four-probe tester.
Example two:
a method for preparing an elemental palladium film by using an atomic layer deposition technology with palladium hexafluoroacetylacetonate Pd (hfac)2 as a palladium precursor and tert-butylhydrazine as a hydrazine reductive precursor comprises the following steps:
s1, heating the atomic layer deposition equipment to a temperature range value of 300 ℃, wherein the limit pressure after vacuumizing is 0.1-10 Pa;
s2, heating the atomic layer deposition system uniformly, wherein the temperature range is 300 ℃, the pressure range is 10-200Pa, the heating time is 40min, and then the flow range of the carrier gas is 10-200 sccm;
s3, opening a pulse valve for atomic layer deposition of palladium hexafluoroacetylacetonate, wherein the opening time of the pulse valve is 50-2000ms, and enabling the palladium hexafluoroacetylacetonate to enter an equipment reaction chamber to be adsorbed and react with the surface of a substrate;
s4, cleaning unreacted hexafluoroacetylacetone palladium and hexafluoroacetylacetone byproducts generated by the reaction by using inert gas as carrier gas, wherein the cleaning time range is 1-200S;
s5, opening a tert-butylhydrazine atomic layer deposition pulse valve, wherein the opening time of the pulse valve is 10-500ms, so that tert-butylhydrazine enters a reaction chamber, and is adsorbed and reacted with the surface of a substrate;
s6, cleaning the reductive precursor which is not completely reacted and the ammonia by-product generated by the reaction by using inert gas as carrier gas;
s7, forming a circulating simple substance palladium film;
s8, the thickness of the simple substance palladium film can be accurately controlled by controlling the circulation times, 500 circulations are carried out, the thickness of the deposited simple substance palladium film is about 23.5nm, and the resistivity of the palladium film is 5.7 mu omega cm by using a four-probe tester.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A method for preparing an elemental palladium film by an atomic layer deposition technology is characterized by comprising the following steps: the method comprises a palladium precursor and a hydrazine-based reducing precursor.
2. The method of claim 1, wherein the atomic layer deposition technique comprises: the palladium precursor can adopt palladium hexafluoroacetylacetone Pd (hfac) 2.
3. The method of claim 1, wherein the atomic layer deposition technique comprises: the hydrazine reductive precursor can adopt a C1-C5 hydrocarbon chain reductive precursor such as anhydrous hydrazine, methyl hydrazine, ethyl hydrazine, propyl hydrazine, tert-butyl hydrazine and the like, and the hydrazine reductive precursor has a structural formula of R1R2N-NR3R4, wherein R1, R2, R3 and R4 comprise hydrogen atoms and C1-C5 hydrocarbon chains, and R1, R2, R3 and R4 can be the same or different.
4. The method for preparing an elemental palladium film by using an atomic layer deposition technology as claimed in claim 1, wherein the reaction temperature of the method is 50-400 ℃, the palladium source Pd (hfac)2 is a palladium precursor, the heating temperature of the palladium source is 120 ℃, the hydrazines are reducing sources, the heating temperature is 30-70 ℃, the heating temperatures of the transport pipeline and the A L D valve are 150-200 ℃, and the precursor source is ensured to be transported in a gas phase without condensation.
5. The method of claim 1, wherein the method comprises the steps of:
s1, heating the atomic layer deposition equipment to a temperature range of 100 ℃ and 400 ℃, wherein the limit pressure after vacuumizing is 0.1-10 Pa;
s2, the atomic layer deposition system is heated uniformly with the temperature range of 100-;
s3, opening a palladium source atomic layer deposition pulse valve, wherein the opening time range of the pulse valve is 50-2000ms, so that a palladium source enters an equipment reaction chamber, and is adsorbed and reacted with the surface of a substrate;
s4, adopting inert gas as carrier gas, cleaning the palladium source which is not completely reacted and hexafluoroacetylacetone by-products generated by the reaction, wherein the cleaning time range is 1-200S;
s5, opening a hydrazine precursor atomic layer deposition pulse valve, wherein the opening time of the pulse valve is 10-500ms, so that the hydrazine precursor enters the reaction chamber, and is adsorbed and reacted with the surface of the substrate;
s6, cleaning the reductive precursor which is not completely reacted and the ammonia by-product generated by the reaction by using inert gas as carrier gas;
s7, forming a circulating simple substance palladium film;
s8, the thickness of the simple substance palladium film can be accurately controlled by controlling the circulation times.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180010248A1 (en) * | 2016-07-08 | 2018-01-11 | Uchicago Argonne, Llc | Functionalized foams |
| CN108642471A (en) * | 2018-04-26 | 2018-10-12 | 江汉大学 | A kind of preparation process and its hydrogen gas sensor of palladium nano-particles film |
| US20200078705A1 (en) * | 2018-09-06 | 2020-03-12 | Uchicago Argonne Llc | Oil skimmer with oleophilic coating |
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- 2020-03-27 CN CN202010230844.0A patent/CN111411345A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180010248A1 (en) * | 2016-07-08 | 2018-01-11 | Uchicago Argonne, Llc | Functionalized foams |
| CN108642471A (en) * | 2018-04-26 | 2018-10-12 | 江汉大学 | A kind of preparation process and its hydrogen gas sensor of palladium nano-particles film |
| US20200078705A1 (en) * | 2018-09-06 | 2020-03-12 | Uchicago Argonne Llc | Oil skimmer with oleophilic coating |
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