CN106835042A - A kind of preparation method of transition metal nitride ultracapacitor coating material - Google Patents
A kind of preparation method of transition metal nitride ultracapacitor coating material Download PDFInfo
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- CN106835042A CN106835042A CN201710027811.4A CN201710027811A CN106835042A CN 106835042 A CN106835042 A CN 106835042A CN 201710027811 A CN201710027811 A CN 201710027811A CN 106835042 A CN106835042 A CN 106835042A
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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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
- 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
- C23C14/0641—Nitrides
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
A kind of preparation method of transition metal nitride ultracapacitor coating material, is related to ultracapacitor.With different deposition pressure reaction magnetocontrol sputtering transition metal nitride ultracapacitor coating materials.The different deposition pressure is 1.0~5.0Pa；The transition metal nitride is ZrN, HfN, NbN.By regulating and controlling the deposition pressure in film deposition process, transition metal nitride can obtain high specific capacitance and be respectively 12.0,13.5 and 10.2mF/cm2, and capability retention up to more than 90% after 20000 times circulate.
Description
Technical field
The present invention relates to ultracapacitor, more particularly, to a kind of transition metal nitride ultracapacitor coating material
Preparation method.
Background technology
As obtainable fossil fuel is increasingly reduced, developing efficient energy storage device turns into the very urgent need of people
Ask.Ultracapacitor, is also called capacitor with super capacity, and its performance is a kind of between battery and conventional electrostatic capacitor
A kind of novel energy storage apparatus of traditional capacitor low energy densities and battery low power density can be made up, with good temperature
The advantages of characteristic, high specific capacitance, high-energy and power density, short charging interval, long service life and energy-conserving and environment-protective, extensively should
Used in the fields such as space flight and aviation, electronic product, compact power, electric automobile ([1] Simon P, Gogotsi
Y.Materials for electrochemical capacitors[J].Nature materials,2008,7(11):
845-854)。
Generally, ultracapacitor is broadly divided into two types according to its charge-storage mechanism：(1) double layer capacitor
(EDLC) electric double layer storage energy, is formed between electrode/electrolyte solution by the reversible adsorption of ion, electrode material is generally
The carbon material of high-specific surface area, such as Graphene, CNT；(2) fake capacitance capacitor, using electrode surface occur can
Inverse faraday's reaction storage energy, electrode material is generally metal oxide, conducting polymer, and the essential distinction of the two is to store up
Difference ([2] Choi D, Blomgren G E, Kumta P N.Fast and reversible surface of energy mode
redox reaction in nanocrystalline vanadium nitride supercapacitors[J]
.Advanced Materials,2006,18(9):1178-1182.).However, specific capacitance it is low be carbon material critical defect.Phase
Than carbon material, metal oxide can be by the reversible faraday's reaction offer in surface specific capacitance higher, but poorly conductive
Limit its power density.For conducting polymer, it is to limit its wide variety of key factor that cyclical stability is low, its
Reason is to cause structural damage ([3] Lu X, Liu T, Zhai T, et al.Improving in the insertion/process of moving out
the Cycling Stability of Metal-Nitride Supercapacitor Electrodes with a Thin
Carbon Shell[J].Advanced Energy Materials,2014,4(4).).Transition metal nitride (ZrN, HfN,
NbN) can be used because it has the advantages that specific capacitance is high, electrical conductivity is high, fusing point is high, chemical stability is good and cycle performance is excellent
It is used as super capacitor material, with potential application prospect.
For transition metal nitride (ZrN, HfN, NbN), prepared by its transition metal nitride (ZrN, HfN, NbN)
Method is a lot, such as simple substance direct nitridation method, oxide carbothermic method, microwave process for synthesizing, magnetron sputtering and chemical vapor deposition
Method.Comparatively speaking, simple substance direct nitridation method, oxide carbothermic method and microwave process for synthesizing, need in preparation process
Temperature higher, while it is difficult to controlling the content of transition nitride surface oxygen；Chemical vapor deposition there is also the slower problem of speed,
And equipment is complicated, the general toxic and contaminative of reacting gas.It is wide using scope and magnetron sputtering has using flexible, film layer
Purity is high, and sedimentation rate is fast, and matrix coating is good, and uniformity it is good, the features such as film-substrate cohesion is strong, film layer planarization is high
([4]H.Hahn,R.Averback.J.Appl.Phys.,67(1990)111.).Achour A etc. use magnetron sputtering method,
N22 and 18sccm and bias are respectively to sputter Ti targets in the environment of -75V with Ar flows, produce Ti atoms or atomic group former with N
Sub- chemical combination forms TiN coatings, and electrochemical Characterization result shows that specific capacitance is up to 8.8mF/cm2, capacity keeps after 20000 circulations
Rate is up to 80% ([5] Achour A, Porto R L, Soussou M A, et al.Titanium nitride films for
micro-supercapacitors:Effect of surface chemistry and film morphology on the
capacitance[J].Journal of Power Sources,2015,300:525-532.).Lucio-Porto R are used
The method of magnetron sputtering prepares VN films, and is analyzed ([6] Lucio- to its chemical property in different electrolyte
Porto R,Bouhtiyya S,Pierson J F,et al.VN thin films as electrode materials
for electrochemical capacitors[J].Electrochimica Acta,2014,141:203-211.)。
The content of the invention
It is an object of the invention to provide a kind of preparation method of transition metal nitride ultracapacitor coating material.
It is of the invention to concretely comprise the following steps：
With different deposition pressure reaction magnetocontrol sputtering transition metal nitride ultracapacitor coating materials.
The different deposition pressure is 1.0~5.0Pa；The transition metal nitride is ZrN, HfN, NbN.
The tool with different deposition pressure reaction magnetocontrol sputtering transition metal nitride ultracapacitor coating materials
Body method can be：Cavity environment temperature is heated to 185 DEG C, deposition chambers background is vacuumized, when chamber pressure≤4.5 ×
10-5After Pa, Ar is passed through, flow set is 45sccm, deposition chamber environmental pressure is adjusted to 1.1Pa, by Zr, Hf, Nb metal
Target power is adjusted to 200W, sputters 10min, and the sputter process process can remove the pollution of the impurity such as target material surface oxide,
Activation target material surface atom, improves the sputter rate and film-substrate cohesion of target, and after sputtering is completed, maintenance cavity temperature is
185 DEG C, heated substrate is to 325 DEG C, then is passed through N2, adjust flow so that Ar and N2Total flow is 65sccm, N2Partial pressure is
0.3Pa, it is 1.0Pa, 2.0Pa, 3.0Pa, 4.0Pa, 5.0Pa that cavity environment pressure is adjusted respectively, rotates sample stage, makes matrix just
To Zr, Hf, Nb metal targets, and it is 100mm with the distance of target, Zr, Hf, Nb target sputtering power is risen into 90W, 3min
After rise to 250W, open target plate washer, the sputtering sedimentation 25min under this power condition, matrix loading back bias voltage in deposition process,
Size is -70V.
The present invention deposits the design side of transition metal nitride (ZrN, HfN, NbN) film layer using reaction magnetocontrol sputtering technology
Method, under the conditions of certain nitrogen partial pressure, temperature etc., by changing deposition pressure, prepares with good combination power, conductance high
Rate, height ratio capacity, transition metal nitride (ZrN, HfN, NbN) ultracapacitor coating material of superior cyclical stability.It is heavy
Transition metal nitride (ZrN, HfN, NbN) film layer prepared by product is presented columnar crystal structure.Electrochemical Characterization result shows, when
When deposition pressure is 4.0Pa, the specific capacitance value of transition metal nitride (ZrN, HfN, NbN) coating is maximum, and by 20000 times
Capability retention is respectively 92.5%, 93.2% and 92.7% after circulation.The present invention was deposited using reaction magnetocontrol sputtering technology
The design of metal nitride (ZrN, HfN, NbN) film layer is crossed, preparation high conductivity, height ratio capacity, superior cyclical stability has been invented
The new method of transition metal nitride (ZrN, HfN, NbN) ultracapacitor coating material.
Brief description of the drawings
Fig. 1 is to prepare the XRD spectra of transition metal nitride ZrN coatings under 1.0Pa and 5.0Pa.
Fig. 2 is to prepare the XRD spectra of transition metal nitride HfN coatings under 1.0Pa and 5.0Pa.
Fig. 3 is to prepare the XRD spectra of transition metal nitride NbN coatings under 1.0Pa and 5.0Pa.
Fig. 4 is respectively under 1.0Pa and 5.0Pa the SEM section shapes for preparing transition metal nitride (ZrN, HfN, NbN) coating
Looks figure.
Fig. 5 is the cycle performance of transition metal nitride (ZrN, HfN, NbN) coating under optimal deposition pressure.
Specific embodiment
Embodiment 1
1st, substrate pretreated
(1) solvent cleaning treatment.First it is cleaned by ultrasonic 20min using acetone, reuses 95% alcohol and be cleaned by ultrasonic 15min,
Again with ultrapure water wash 5min after taking-up.
(2) ion gun Bombardment and cleaning treatment.Clear 10min is carried out to matrix using Hall ion guns, environmental pressure is 2.3 ×
10-2Pa, Ar flow are 12sccm, and substrate bias are -120V, and cathode current is 31A, and cathode voltage is 26V, and anode current is
7.5A, anode voltage is 70V.
2nd, with 1.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride ZrN coatings
(1) Zr metal targets pre-sputtering.Cavity environment temperature is heated 185 DEG C, two grades of dresses of mechanical pump and molecular pump are used
Put and vacuumize deposition chambers background, when chamber pressure≤4.5 × 10-5After Pa, Ar is passed through, flow set is 45sccm, adjusted
Operating pressure, by Zr metal targets power adjusting to 200W, pre-processes 10min to 1.1Pa in cavity.The pre-sputtering process is used to
The pollution of the impurity such as target material surface oxide is removed, target material surface atom is activated, the sputtering of target is also improved while improving purity
Speed.
(2) transition metal nitride ZrN coatings are deposited.After pre-sputtering is completed, it is 185 DEG C, matrix to maintain cavity temperature
Temperature is 325 DEG C, then is passed through N2, adjust flow so that Ar and N2Total flow is 65sccm, N2Partial pressure is 0.3Pa, chamber pressure
It is 1.0Pa.Sample stage is rotated, makes matrix just to Zr metal targets, and be 100mm with the distance of target, by Zr target d.c. sputterings
Power rises to 90W, and 250W is risen to after 3min, opens target plate washer, sputtering sedimentation 25min, deposition process under this power condition
Middle matrix loads back bias voltage, and size is -70V.
3rd, the phase structure of the ZrN coatings under 1.0Pa deposition pressures is characterized using X-ray diffraction (XRD).Fig. 2 is heavy for 1.0Pa
The XRD spectra of the ZrN films under power is overstock, shows that, when deposition pressure is 1.0Pa, ZrN layers has face-centred cubic structure, is
(200) it is orientated.
4th, SEM coating structures observation
Fig. 3 is the SEM cross-section morphology figures that ZrN coatings are prepared under respectively 1.0Pa and 5.0Pa, and deposition pressure is 1.0Pa
When, ZrN films are presented columnar crystal structure, and growth is continuous.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of ZrN coatings under different deposition pressures, when deposition pressure is for 1.0Pa, the ratio of ZrN
Capacitance 4.2mF/cm2。
Table 1
Embodiment 2
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 2.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride ZrN coatings
(1) Zr metal targets pre-sputtering.With embodiment 1.
(2) transition metal nitride ZrN coatings are deposited.Chamber pressure is changed to 2.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the ZrN coatings under 2.0Pa deposition pressures is characterized using X-ray diffraction (XRD).With embodiment 1.
4th, SEM coating structures observation
With embodiment 1.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of ZrN coatings under different deposition pressures, when deposition pressure is for 2.0Pa, the ratio of ZrN
Capacitance 6.5mF/cm2。
Embodiment 3
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 3.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride ZrN coatings
(1) Zr metal targets pre-sputtering.With embodiment 1.
(2) transition metal nitride ZrN coatings are deposited.Chamber pressure is changed to 3.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the ZrN coatings under 3.0Pa deposition pressures is characterized using X-ray diffraction (XRD).With embodiment 1.
4th, SEM coating structures observation
With embodiment 1.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of ZrN coatings under different deposition pressures, when deposition pressure is for 3.0Pa, the ratio of ZrN
Capacitance 7.9mF/cm2。
Embodiment 4
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 4.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride ZrN coatings
(1) Zr metal targets pre-sputtering.With embodiment 1.
(2) transition metal nitride ZrN coatings are deposited.Chamber pressure is changed to 4.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the ZrN coatings under 4.0Pa deposition pressures is characterized using X-ray diffraction (XRD).With embodiment 1.
4th, SEM coating structures observation
With embodiment 1.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of ZrN coatings under different deposition pressures, when deposition pressure is for 4.0Pa, the ratio of ZrN
Capacitance 12.0mF/cm2.The cycle performance of ZrN coatings under Fig. 4 optimal deposition pressure, ZrN specific capacities after circulating 20000 times
Conservation rate is up to 92.5%.
Embodiment 5
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 5.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride ZrN coatings
(1) Zr metal targets pre-sputtering.With embodiment 1.
(2) transition metal nitride ZrN coatings are deposited.Chamber pressure is changed to 5.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the ZrN coatings under 5.0Pa deposition pressures is characterized using X-ray diffraction (XRD).Fig. 2 is heavy for 5.0Pa
The XRD spectra of the ZrN films under power is overstock, ZrN layers has face-centred cubic structure, be (111) orientation.
4th, SEM coating structures observation
Fig. 3 is the SEM cross-section morphology figures that ZrN coatings are prepared under respectively 1.0Pa and 5.0Pa, and deposition pressure is 5.0Pa
When, ZrN films are presented columnar crystal structure, and growth is continuous.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of ZrN coatings under different deposition pressures, when deposition pressure is for 5.0Pa, the ratio of ZrN
Capacitance 7.5mF/cm2。
Embodiment 6
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 1.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride HfN coatings
(1) Hf metal targets pre-sputtering.Metal targets are changed to Hf metal targets, other steps are with embodiment 1.
(2) transition metal nitride HfN coatings are deposited.Metal targets are changed to Hf metal targets, other steps are with implementation
Example 1.
3rd, the phase structure of the HfN coatings under 1.0Pa deposition pressures is characterized using X-ray diffraction (XRD).Fig. 2 is heavy for 1.0Pa
The XRD spectra of the HfN films under power is overstock, HfN layers has face-centred cubic structure, be (111) orientation.
4th, SEM coating structures observation
Fig. 3 is the SEM cross-section morphology figures that HfN coatings are prepared under respectively 1.0Pa and 5.0Pa, and deposition pressure is 1.0Pa
When, HfN films are presented fine and closely woven columnar crystal structure, and growth is continuous.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of HfN coatings under different deposition pressures, when deposition pressure is for 1.0Pa, the ratio of HfN
Capacitance 4.8mF/cm2。
Embodiment 7
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 2.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride HfN coatings
(1) Hf metal targets pre-sputtering.Metal targets are changed to Hf metal targets, other steps are with embodiment 1.
(2) transition metal nitride HfN coatings are deposited.Metal targets are changed to Hf metal targets, while chamber pressure changes
It is 2.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the HfN coatings under 2.0Pa deposition pressures is characterized using X-ray diffraction (XRD).With embodiment 1.
4th, SEM coating structures observation
With embodiment 1.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of HfN coatings under different deposition pressures, when deposition pressure is for 2.0Pa, the ratio of HfN
Capacitance 7.2mF/cm2。
Embodiment 8
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 3.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride HfN coatings
(1) Hf metal targets pre-sputtering.Metal targets are changed to Hf metal targets, other steps are with embodiment 1.
(2) transition metal nitride HfN coatings are deposited.Metal targets are changed to Hf metal targets, while chamber pressure changes
It is 3.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the HfN coatings under 3.0Pa deposition pressures is characterized using X-ray diffraction (XRD).With embodiment 1.
4th, SEM coating structures observation
With embodiment 1.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of HfN coatings under different deposition pressures, when deposition pressure is for 3.0Pa, the ratio of HfN
Capacitance 8.6mF/cm2。
Embodiment 9
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 4.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride HfN coatings
(1) Hf metal targets pre-sputtering.Metal targets are changed to Hf metal targets, other steps are with embodiment 1.
(2) transition metal nitride HfN coatings are deposited.Metal targets are changed to Hf metal targets, while chamber pressure changes
It is 4.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the HfN coatings under 4.0Pa deposition pressures is characterized using X-ray diffraction (XRD).With embodiment 1.
4th, SEM coating structures observation
With embodiment 1.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of HfN coatings under different deposition pressures, when deposition pressure is for 4.0Pa, the ratio of HfN
Capacitance 13.5mF/cm2.The cycle performance of HfN coatings under Fig. 4 optimal deposition pressure, HfN specific capacities after circulating 20000 times
Conservation rate is up to 93.2%.
Embodiment 10
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 5.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride HfN coatings
(1) Hf metal targets pre-sputtering.Metal targets are changed to Hf metal targets, other steps are with embodiment 1.
(2) transition metal nitride HfN coatings are deposited.Metal targets are changed to Hf metal targets, while chamber pressure changes
It is 5.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the HfN coatings under 5.0Pa deposition pressures is characterized using X-ray diffraction (XRD).Fig. 2 is heavy for 5.0Pa
The XRD spectra of the HfN films under power is overstock, HfN layers has fine and closely woven face-centred cubic structure, be (111) orientation.
4th, SEM coating structures observation
Fig. 3 is the SEM cross-section morphology figures that HfN coatings are prepared under respectively 1.0Pa and 5.0Pa, and deposition pressure is 5.0Pa
When, HfN films are presented fine and closely woven columnar crystal structure, and growth is continuous.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of HfN coatings under different deposition pressures, when deposition pressure is for 5.0Pa, the ratio of HfN
Capacitance 9.4mF/cm2。
Embodiment 11
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 1.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride NbN coatings
(1) Nb metal targets pre-sputtering.Metal targets are changed to Nb metal targets, other steps are with embodiment 1.
(2) transition metal nitride NbN coatings are deposited.Metal targets are changed to Nb metal targets, other steps are with implementation
Example 1.
3rd, the phase structure of the NbN coatings under 1.0Pa deposition pressures is characterized using X-ray diffraction (XRD).Fig. 2 is heavy for 1.0Pa
The XRD spectra of the NbN films under power is overstock, NbN layers has face-centred cubic structure, be (111) orientation.
4th, SEM coating structures observation
Fig. 3 is the SEM cross-section morphology figures that NbN coatings are prepared under respectively 1.0Pa and 5.0Pa, and deposition pressure is 1.0Pa
When, NbN films are presented columnar crystal structure, and growth is continuous.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of NbN coatings under different deposition pressures, when deposition pressure is for 1.0Pa, the ratio of NbN
Capacitance 3.5mF/cm2。
Embodiment 12
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 2.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride NbN coatings
(1) Nb metal targets pre-sputtering.Metal targets are changed to Nb metal targets, other steps are with embodiment 1.
(2) transition metal nitride NbN coatings are deposited.Metal targets are changed to Nb metal targets, while chamber pressure changes
It is 2.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the NbN coatings under 2.0Pa deposition pressures is characterized using X-ray diffraction (XRD).With embodiment 1.
4th, SEM coating structures observation
With embodiment 1.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of NbN coatings under different deposition pressures, when deposition pressure is for 2.0Pa, the ratio of NbN
Capacitance 5.6mF/cm2。
Embodiment 13
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 3.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride NbN coatings
(1) Nb metal targets pre-sputtering.Metal targets are changed to Nb metal targets, other steps are with embodiment 1.
(2) transition metal nitride NbN coatings are deposited.Metal targets are changed to Nb metal targets, while chamber pressure changes
It is 3.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the NbN coatings under 3.0Pa deposition pressures is characterized using X-ray diffraction (XRD).With embodiment 1.
4th, SEM coating structures observation
With embodiment 1.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of NbN coatings under different deposition pressures, when deposition pressure is for 3.0Pa, the ratio of NbN
Capacitance 6.3mF/cm2。
Embodiment 14
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 4.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride NbN coatings
(1) Nb metal targets pre-sputtering.Metal targets are changed to Nb metal targets, other steps are with embodiment 1.
(2) transition metal nitride NbN coatings are deposited.Metal targets are changed to Nb metal targets, while chamber pressure changes
It is 4.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the NbN coatings under 4.0Pa deposition pressures is characterized using X-ray diffraction (XRD).With embodiment 1.
4th, SEM coating structures observation
With embodiment 1.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of NbN coatings under different deposition pressures, when deposition pressure is for 4.0Pa, the ratio of NbN
Capacitance 10.2mF/cm2.The cycle performance of NbN coatings under Fig. 4 optimal deposition pressure, NbN specific capacities after circulating 20000 times
Conservation rate is up to 92.7%.
Embodiment 15
1st, substrate pretreated
(1) solvent cleaning treatment.With embodiment 1.
(2) ion gun Bombardment and cleaning treatment.With embodiment 1.
2nd, with 5.0Pa deposition pressure reaction magnetocontrol sputtering transition metal nitride NbN coatings
(1) Nb metal targets pre-sputtering.Metal targets are changed to Nb metal targets, other steps are with embodiment 1.
(2) transition metal nitride NbN coatings are deposited.Metal targets are changed to Nb metal targets, while chamber pressure changes
It is 5.0Pa, other steps are with embodiment 1.
3rd, the phase structure of the NbN coatings under 5.0Pa deposition pressures is characterized using X-ray diffraction (XRD).Fig. 2 is heavy for 5.0Pa
The XRD spectra of the NbN films under power is overstock, NbN layers has face-centred cubic structure, be (200) orientation.
4th, SEM coating structures observation
Fig. 3 is the SEM cross-section morphology figures that NbN coatings are prepared under respectively 1.0Pa and 5.0Pa, and deposition pressure is 5.0Pa
When, NbN films are presented columnar crystal structure, and growth is continuous.
5th, electrical performance testing
Table 1 is prepares the specific capacitance value of NbN coatings under different deposition pressures, when deposition pressure is for 5.0Pa, the ratio of NbN
Capacitance 7.1mF/cm2。
The XRD spectra of transition metal nitride ZrN coatings is prepared under 1.0Pa and 5.0Pa referring to Fig. 1.1.0Pa and 5.0Pa
The lower XRD spectra for preparing transition metal nitride HfN coatings is referring to Fig. 2.Transition metal nitride is prepared under 1.0Pa and 5.0Pa
The XRD spectra of NbN coatings is referring to Fig. 3.Transition metal nitride (ZrN, HfN, NbN) coating is prepared under 1.0Pa and 5.0Pa
SEM cross-section morphology figures are referring to Fig. 4.The cycle performance of transition metal nitride (ZrN, HfN, NbN) coating under optimal deposition pressure
Referring to Fig. 5.
Claims (4)
1. a kind of preparation method of transition metal nitride ultracapacitor coating material, it is characterised in that it is concretely comprised the following steps：
With different deposition pressure reaction magnetocontrol sputtering transition metal nitride ultracapacitor coating materials.
2. a kind of preparation method of transition metal nitride ultracapacitor coating material as claimed in claim 1, its feature exists
In the different deposition pressure be 1.0~5.0Pa.
3. a kind of preparation method of transition metal nitride ultracapacitor coating material as claimed in claim 1, its feature exists
In the transition metal nitride be ZrN, HfN, NbN.
4. a kind of preparation method of transition metal nitride ultracapacitor coating material as claimed in claim 1, its feature exists
In the specific method with different deposition pressure reaction magnetocontrol sputtering transition metal nitride ultracapacitor coating materials
For：Cavity environment temperature is heated to 185 DEG C, deposition chambers background is vacuumized, when chamber pressure≤4.5 × 10-5After Pa, lead to
Enter Ar, flow set is 45sccm, regulation deposition chamber environmental pressure to 1.1Pa adjusts Zr, Hf, Nb metal targets power
Section sputters 10min to 200W, and after sputtering is completed, it is 185 DEG C to maintain cavity temperature, and heated substrate is to 325 DEG C, then is passed through N2,
Regulation flow so that Ar and N2Total flow is 65sccm, N2Partial pressure is 0.3Pa, adjust respectively cavity environment pressure be 1.0Pa,
2.0Pa, 3.0Pa, 4.0Pa, 5.0Pa, rotate sample stage, make matrix just to Zr, Hf, Nb metal targets, and with the distance of target
It is 100mm, Zr, Hf, Nb target sputtering power is risen into 90W, 250W is risen to after 3min, target plate washer is opened, in this power
Under the conditions of sputtering sedimentation 25min, in deposition process matrix loading back bias voltage, size be -70V.
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| CN108198698A (en) * | 2018-02-11 | 2018-06-22 | 广州大学 | A kind of high power capacity transition metal nitride coating electrode material and preparation method thereof |
| CN108642446A (en) * | 2018-06-01 | 2018-10-12 | 广东工业大学 | A kind of porous C rN coatings and preparation method thereof and a kind of ultracapacitor |
| CN108831754A (en) * | 2018-06-22 | 2018-11-16 | 广东工业大学 | A kind of MeN coating of high-specific surface area and preparation method thereof and supercapacitor |
| RU2709487C1 (en) * | 2018-08-14 | 2019-12-18 | Общество с ограниченной ответственностью "Финика" | Solid-state thin-film hybrid electrochemical current source |
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| CN112831768A (en) * | 2021-01-04 | 2021-05-25 | 南京佑天金属科技有限公司 | Preparation method and application of hafnium nitride film with high crystallization quality |
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