CN115233159B - Silver film with low roughness and controllable dielectric constant and preparation method thereof - Google Patents
Silver film with low roughness and controllable dielectric constant and preparation method thereof Download PDFInfo
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- CN115233159B CN115233159B CN202210942761.3A CN202210942761A CN115233159B CN 115233159 B CN115233159 B CN 115233159B CN 202210942761 A CN202210942761 A CN 202210942761A CN 115233159 B CN115233159 B CN 115233159B
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 260
- 239000004332 silver Substances 0.000 title claims abstract description 260
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 257
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000004544 sputter deposition Methods 0.000 claims abstract description 124
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 31
- 238000000151 deposition Methods 0.000 claims abstract description 24
- 229910052786 argon Inorganic materials 0.000 claims abstract description 23
- 239000013077 target material Substances 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 13
- 230000001105 regulatory effect Effects 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000003746 surface roughness Effects 0.000 abstract description 16
- 239000010408 film Substances 0.000 description 174
- 230000008569 process Effects 0.000 description 13
- 238000003384 imaging method Methods 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 150000003378 silver Chemical class 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
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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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
-
- 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
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- 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
- C23C14/54—Controlling or regulating the coating process
- C23C14/548—Controlling the composition
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The disclosure provides a silver film with low roughness and controllable dielectric constant and a preparation method thereof, wherein the preparation method of the silver film comprises the following steps: s1, introducing mixed gas of argon and nitrogen into a vacuum cavity, adjusting sputtering power of a silver target and aluminum nitride target, and jointly performing sputtering deposition to prepare a plurality of silver films under different sputtering powers; s2, obtaining a plurality of dielectric constant-wavelength curves of a plurality of silver films; s3, determining the first sputtering power of the silver target and the second sputtering power of the aluminum nitride target according to a plurality of dielectric constant-wavelength curves based on the target dielectric constant of the target silver film under a specific wavelength; and S4, introducing mixed gas of argon and nitrogen into the vacuum cavity, using first sputtering power for the silver target material and second sputtering power for the aluminum nitride target material, and depositing to prepare the low-roughness silver film under the target dielectric constant. According to the method disclosed by the invention, the dielectric constant of the silver film is regulated and controlled through the doping of aluminum nitride, and meanwhile, the surface roughness of the silver film is obviously reduced.
Description
Technical Field
The disclosure relates to the technical field of metal film performance regulation, in particular to a silver film with low roughness and controllable dielectric constant and a preparation method thereof.
Background
The silver film, which is a super-diffraction film layer, generates localized plasmons near the surface thereof, and thus is widely used in the fields of photoelectric sensors and super-diffraction optical imaging. In practical cases, the surface localized plasmon behavior of a silver film is determined by its complex dielectric constant and surface roughness together. The surface roughness of the silver film is increased to cause the turbulence of the surface plasmon field and harm the optical characteristics of the silver film as a super diffraction lens, so that the smaller the surface roughness of the silver film is, the better the surface roughness is in most application scenes; the complex dielectric constant of the silver film determines parameters such as sensitivity and figure of merit of the surface plasmon. In practical application, the complex dielectric constant of the silver film may be required to reach a specific optimal range, so that the surface plasmon behavior of the silver film meets different technical requirements, and the optimal sensing sensitivity or the optimal super-diffraction imaging effect is achieved.
In general, the film forming process of silver on the surface of a silicon wafer is three-dimensional growth, and the surface roughness of a polycrystalline silver film prepared by a physical vapor method is larger; and, at a fixed growth temperature, the silver film prepared by the physical vapor deposition method has a definite dielectric constant-wavelength function, i.e., at a specific incident wavelength, the real part and the imaginary part of the dielectric constant of the silver film are fixed.
Therefore, a new technical route is needed to be developed to reduce the surface roughness of the silver film, and simultaneously realize the regulation and control of the real part and the imaginary part of the composite dielectric constant of the silver film, so that the silver film is suitable for wider practical requirements.
Disclosure of Invention
First, the technical problem to be solved
Aiming at the problems, the disclosure provides a silver film with low roughness and controllable dielectric constant and a preparation method thereof, which are used for solving the technical problems that the dielectric constant of the silver film is difficult to regulate and control by the traditional method, the roughness of the obtained silver film is high, and the like.
(II) technical scheme
In one aspect, the disclosure provides a method for preparing a silver film with low roughness and controllable dielectric constant, comprising: s1, introducing mixed gas of argon and nitrogen into a vacuum cavity, adjusting sputtering power of a silver target and aluminum nitride target, and jointly performing sputtering deposition to prepare a plurality of silver films under different sputtering powers; s2, obtaining a plurality of dielectric constant-wavelength curves of a plurality of silver films; s3, determining the first sputtering power of the silver target and the second sputtering power of the aluminum nitride target according to a plurality of dielectric constant-wavelength curves based on the target dielectric constant of the target silver film under a specific wavelength; and S4, introducing mixed gas of argon and nitrogen into the vacuum cavity, using first sputtering power for the silver target material and second sputtering power for the aluminum nitride target material, and depositing to prepare the low-roughness silver film under the target dielectric constant.
Further, the step of introducing the mixed gas of argon and nitrogen into the vacuum cavity in S1 comprises the following steps: vacuumizing the cavity to form a vacuum cavity; and (3) introducing mixed gas of argon and nitrogen into the vacuum cavity, wherein the regulating range of the working cavity pressure is 1.0 mTorr-5.0 mTorr.
Further, the volume ratio of nitrogen in the mixed gas of argon and nitrogen is 20-100%.
Further, in S1, adjusting sputtering power of the silver target and the aluminum nitride target, and co-sputtering deposition to prepare a plurality of silver films under different sputtering powers includes: pre-sputtering a silver target and an aluminum nitride target to remove surface impurities; sputtering silver target material by using direct current sputtering, and sputtering aluminum nitride target material by using radio frequency sputtering, and jointly sputtering and depositing silver film on the substrate; and adjusting the power of direct current sputtering and the power of radio frequency sputtering, and depositing and preparing a plurality of silver films under different sputtering powers.
Further, the thicknesses of the plurality of silver films are equal, and the thickness range of the silver film is 10nm to 100nm.
Further, the method is applied to 4-inch magnetron sputtering equipment, the power of direct current sputtering is 50-400W, and the power of radio frequency sputtering is 80-400W.
Further, the surface material of the substrate comprises Si, siO 2 One of Ge, siBARC, znO.
Further, S2 includes: collecting dielectric constant data of each silver film under different wavelengths by using an ellipsometer; and fitting the dielectric constant data at different wavelengths to obtain a dielectric constant-wavelength curve of each silver film.
Further, according to the target dielectric constant of the target silver film under the specific wavelength, determining a first dielectric constant-wavelength curve corresponding to the specific wavelength and the target dielectric constant in the multiple dielectric constant-wavelength curves; and determining the first sputtering power of the silver target and the second sputtering power of the aluminum nitride target according to the first dielectric constant-wavelength curve.
Another aspect of the present disclosure provides a low roughness and dielectric constant controllable silver film prepared according to the foregoing method for preparing a low roughness and dielectric constant controllable silver film.
(III) beneficial effects
According to the silver film with low roughness and controllable dielectric constant and the preparation method thereof, the sputtering power of the silver target material and the aluminum nitride target material is adjusted to adjust the doping concentration of aluminum nitride in the silver film, so that the dielectric constant-wavelength curve of the silver film is regulated; when the method is applied, the corresponding dielectric constant-wavelength curve is determined according to the target dielectric constant of the target silver film under the specific wavelength, so that the sputtering power of the silver target and the aluminum nitride target is determined, and the low-roughness silver film under the target dielectric constant can be prepared according to the sputtering power. The method disclosed by the invention realizes the regulation and control of the dielectric constant of the silver film, effectively reduces the surface roughness of the silver film and greatly expands the application range of the silver film in photoelectric devices.
Drawings
FIG. 1 schematically illustrates a flow chart of a method of preparing a low roughness and dielectric constant controllable silver film in accordance with an embodiment of the present disclosure;
fig. 2 schematically illustrates an apparatus structure diagram for preparing a silver film by co-sputtering a silver target and an aluminum nitride target according to an embodiment of the present disclosure;
fig. 3 schematically illustrates a silver film surface topography (a) prepared by co-sputtering a silver target and an aluminum nitride target and a silver film surface topography (b) prepared by a conventional method (pure silver target sputtering) according to an embodiment of the present disclosure;
FIG. 4 schematically illustrates a graph comparing dielectric constant versus wavelength functions of a silver film prepared by co-sputtering a silver target with an aluminum nitride target in an embodiment of the present disclosure with a silver film prepared by a conventional method (pure silver target sputtering);
FIG. 5 schematically illustrates a graph of real and imaginary parts (at 365 nm) of dielectric constant of a prepared silver film as a function of sputtering power of an aluminum nitride target, according to a sputtering power of a fixed silver target in an embodiment of the present disclosure;
fig. 6 schematically illustrates a comparison of lithography exposure imaging effects when a silver film prepared by co-sputtering a silver target and an aluminum nitride target and a silver film prepared by a conventional method (pure silver target sputtering) are used as a super diffraction layer in an embodiment of the present disclosure.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The terms "comprises," "comprising," and/or the like, as used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components.
The use of ordinal numbers such as "first," "second," "third," etc., in the description and the claims to modify a corresponding element does not by itself connote or represent any ordinal number of elements, nor does it represent the order in which an element is joined to another element or the order in which it is manufactured, but rather the ordinal numbers are used merely to distinguish one element having a certain name from another element having a same name.
The embodiment of the disclosure provides a method for preparing a silver film with low roughness and controllable dielectric constant, please refer to fig. 1, which includes: s1, introducing mixed gas of argon and nitrogen into a vacuum cavity, adjusting sputtering power of a silver target and aluminum nitride target, and jointly performing sputtering deposition to prepare a plurality of silver films under different sputtering powers; s2, obtaining a plurality of dielectric constant-wavelength curves of a plurality of silver films; s3, determining the first sputtering power of the silver target and the second sputtering power of the aluminum nitride target according to a plurality of dielectric constant-wavelength curves based on the target dielectric constant of the target silver film under a specific wavelength; and S4, introducing mixed gas of argon and nitrogen into the vacuum cavity, using first sputtering power for the silver target material and second sputtering power for the aluminum nitride target material, and depositing to prepare the low-roughness silver film under the target dielectric constant.
The method and the device enable the silver target and the aluminum nitride target to be co-sputtered, and adjust the doping concentration of aluminum nitride in the silver film by adjusting the sputtering power of the silver target and the aluminum nitride target, so as to adjust and control the dielectric constant-wavelength curve of the silver film; when the method is applied, the corresponding dielectric constant-wavelength curve is determined according to the target dielectric constant of the target silver film under the specific wavelength, so that the sputtering power of the silver target and the aluminum nitride target is determined, and the silver film under the target dielectric constant can be prepared according to the sputtering power. The doping of aluminum nitride also changes the growth mode of silver atoms on the substrate to be plated, and can effectively reduce the surface roughness of the silver film. The method disclosed by the invention realizes the regulation and control of the dielectric constant of the silver film, has better surface morphology, and greatly expands the application range of the silver film in photoelectric devices.
Based on the above embodiment, introducing the mixed gas of argon and nitrogen into the vacuum chamber in S1 includes: vacuumizing the cavity to form a vacuum cavity; and (3) introducing mixed gas of argon and nitrogen into the vacuum cavity, wherein the regulating range of the working cavity pressure is 1.0 mTorr-5.0 mTorr.
Before silver film deposition, the deposition cavity is pumped to high vacuum by using a molecular pump and other equipment, and then the mixed gas of argon and nitrogen is introduced into the vacuum cavity, so that the working cavity pressure is regulated and controlled to be 1.0 mTorr-5.0 mTorr. The nitrogen is mainly used for supplementing nitrogen atoms lost by the aluminum nitride target in the vacuum coating process, and the argon is mainly used for bombarding the target and adjusting the cavity pressure.
Based on the embodiment, the volume ratio of nitrogen in the mixed gas of argon and nitrogen is 20-100%. Further preferably, the volume ratio of nitrogen in the mixed gas of argon and nitrogen is 40% -70%.
Preferably, the volume ratio of the nitrogen in the mixed gas can be adjusted between 20% and 100%, and the pressure ratio of the argon to the nitrogen can be adjusted by the threshold value of the two paths of gases. The volume ratio of nitrogen in the mixed gas can influence the stoichiometric number of aluminum nitride doped in the silver film (namely the number ratio of nitrogen atoms and aluminum atoms actually doped into the silver film), and the dielectric constant of the prepared silver film can be finely adjusted by adjusting the volume ratio of nitrogen in the mixed gas on the premise of a certain sputtering power.
In the silver film preparation method disclosed by the disclosure, the doping concentration of aluminum nitride plays a main role in regulating and controlling the dielectric constant of the silver film. The sputtering power of the two targets can be adjusted according to the required film growth speed and the required aluminum nitride doping concentration, and the growth speed will mainly influence the surface roughness of the film, and the aluminum nitride doping concentration will influence the dielectric constant of the film.
On the basis of the above embodiment, adjusting the sputtering power of the silver target and the aluminum nitride target in S1, and co-sputtering deposition to prepare a plurality of silver films under different sputtering powers includes: pre-sputtering a silver target and an aluminum nitride target to remove surface impurities; sputtering silver target material by using direct current sputtering, and sputtering aluminum nitride target material by using radio frequency sputtering, and jointly sputtering and depositing silver film on the substrate; and adjusting the power of direct current sputtering and the power of radio frequency sputtering, and depositing and preparing a plurality of silver films under different sputtering powers.
Before sputtering deposition coating, respectively pre-sputtering a silver target and an aluminum nitride target (the purities of the silver target and the aluminum nitride target are over 99.99 percent) under certain sputtering power to remove impurities on the surface of the target; and then simultaneously opening a baffle plate and a power supply of the silver target and the aluminum nitride target, sputtering the silver target by using direct current and the aluminum nitride target by using radio frequency, and jointly sputtering and depositing a silver film on the substrate. The relative sputtering rates of the silver target and the aluminum nitride target can be adjusted by adjusting the power of the silver target and the aluminum nitride target, so that the doping concentration of aluminum nitride is influenced, and the composite dielectric constants of the silver films are regulated and controlled by controlling the doping concentration of aluminum nitride, so that a plurality of silver films with different dielectric constants can be prepared by deposition, wherein the dielectric constants comprise real part numerical values and imaginary part numerical values of the composite dielectric constants under different incident light wavelengths.
Based on the above embodiments, the thicknesses of the plurality of silver films are equal, and the thickness of the silver film ranges from 10nm to 100nm.
The thickness of the silver film is not too thin, otherwise, the silver film may not form a continuous film, and various physical properties are seriously degraded; the thickness of the silver film is not too thick, otherwise, the dielectric constant of the silver film is hard to be characterized by the existing means, and the silver film has no reference property.
The thickness of the silver film is controlled by controlling the sputtering time, namely, a silver film test piece is prepared under certain technological parameters and sputtering time, the thickness of the test piece is characterized by an ellipsometer, and the sputtering time required for preparing the silver film with specific thickness under the technological parameters is calculated. The silver films prepared under different processes are controlled to be in the same thickness, so that the influence of thickness variation on the dielectric constant of the silver film is eliminated.
Based on the embodiment, the method is applied to 4-inch magnetron sputtering equipment, the power of direct current sputtering is 50-400W, and the power of radio frequency sputtering is 80-400W.
The aluminum nitride target uses a radio frequency power supply, and the sputtering efficiency is low, so that the micro doping of silver can be realized under the power of 80-400W. The power range is suitable for a 4-inch magnetron sputtering device, such as a coating device with smaller or larger size, and the power value of the power supply used can be correspondingly reduced or increased.
On the basis of the embodiment, the surface material of the substrate comprises Si, siO 2 And Ge, siBARC, znO.
The preparation method disclosed by the invention is widely applicable to the surface materials of the substrate, and can be used for preparing the silver film with adjustable dielectric constant on the surfaces of different material types, such as the materials.
On the basis of the above embodiment, S2 includes: collecting dielectric constant data of each silver film under different wavelengths by using an ellipsometer; and fitting the dielectric constant data at different wavelengths to obtain a dielectric constant-wavelength curve of each silver film.
After the preparation of the silver film is completed, measuring the real part and the imaginary part of the dielectric constants of different incident light wavelengths by using an ellipsometer for each silver film sample, fitting the obtained data of the real part and the imaginary part of the dielectric constants, and drawing to obtain a change curve of the dielectric constants along with the incident light wavelengths, thereby obtaining a plurality of dielectric constant-wavelength curves. The dielectric constant-wavelength curve includes a curve of a real part of dielectric constant with respect to a wavelength of incident light and a curve of an imaginary part of dielectric constant with respect to a wavelength of incident light.
On the basis of the above embodiment, S3 includes: determining a first dielectric constant-wavelength curve corresponding to the specific wavelength and the target dielectric constant in the multiple dielectric constant-wavelength curves according to the target dielectric constant of the target silver film under the specific wavelength; and determining the first sputtering power of the silver target and the second sputtering power of the aluminum nitride target according to the first dielectric constant-wavelength curve.
According to the target dielectric constant of the target silver film under the specific wavelength, a first dielectric constant-wavelength curve corresponding to the target silver film can be determined from the obtained multiple dielectric constant-wavelength curves, namely, the curve of the point corresponding to the specific wavelength and the target dielectric constant. Each dielectric constant-wavelength curve corresponds to the sputtering power of a group of silver targets and aluminum nitride targets, and the required first sputtering power of the silver targets and the required second sputtering power of the aluminum nitride targets can be determined according to the first dielectric constant-wavelength curve.
The disclosure also provides a silver film with low roughness and controllable dielectric constant, which is prepared according to the preparation method of the silver film with low roughness and controllable dielectric constant.
According to the preparation method of the silver film, a series of silver films under different process parameters are prepared by adjusting the co-sputtering power of the silver target and the aluminum nitride target and the gas nitrogen content in the cavity in the film coating process, the change curves of the dielectric constant real part and the imaginary part of the series of silver films along with the wavelength of incident light are obtained by analysis and drawing, the process parameters for preparing the target silver films are selected and prepared by taking the change curves as references, the composite dielectric constant controllability of the silver films is finally and effectively realized, the technical problem that the dielectric constant real part and the imaginary part of the same metal film are difficult to regulate and control is solved, and the application range of the silver metal film is expanded; meanwhile, compared with the silver film prepared by the traditional film coating method, the silver film prepared by the method has obviously reduced surface roughness, has better surface morphology and can widen the practical application range of the silver film. Further, the preparation method disclosed by the disclosure can be further expanded to the category of regulating other optical properties of the silver film, such as refractive index, transmittance and the like.
The present disclosure is further illustrated by the following detailed description. The silver film with the low roughness and the controllable dielectric constant and the preparation method thereof are specifically described in the following examples. However, the following examples are merely illustrative of the present disclosure, and the scope of the present disclosure is not limited thereto.
The preparation method of the silver film with low roughness and controllable dielectric constant comprises the following steps: and selecting a technological parameter range for preparing the target silver film based on the real part and the imaginary part of the expected dielectric constant of the target silver film under a specific incident wavelength, wherein the technological parameter range comprises the power used by a silver target and an aluminum nitride target and the nitrogen content in growth gas, and preparing the target silver film. In the silver coating process, silver and aluminum nitride are co-sputtered with certain power to regulate and control the dielectric constant-wavelength function of the silver film, so that the real part and the imaginary part of the dielectric constant of the silver film under specific wavelength can reach different values from those of the traditional silver film; compared with the prior art, the surface roughness of a series of silver films prepared by the process is obviously reduced, and the preparation method comprises the following specific steps:
step 1: placing a substrate to be coated into a deposition cavity of a magnetron sputtering device, and controlling the substrate and a target to rotate at a certain speed, wherein the material on the surface of the substrate can be Si or SiO 2 Ge, siBARC, znO, etc.
Step 2: pumping the cavity to high vacuum by using a molecular pump to ensure that the cavity pressure is less than 1 x 10 -6 Torr。
Step 3: and introducing mixed gas of argon and nitrogen into the high-vacuum cavity, wherein the pressure of the working cavity is regulated and controlled to be 1.0 mTorr-5.0 mTorr. The nitrogen is used for supplementing nitrogen atoms lost by the aluminum nitride target in the vacuum coating process, the volume ratio of the nitrogen in the growth gas can be adjusted between 20% and 100%, and the pressure ratio of the two gases can be adjusted through the valve control values of the two gases.
Step 4: before sputtering deposition coating, pre-sputtering a silver target and an aluminum nitride target (the purities of the silver target and the aluminum nitride target are more than 99.99 percent) for 60-300 seconds under the power of 50-400W and 80-400W respectively to remove impurities on the surface of the target; then, a baffle plate and a power supply of the silver target and the aluminum nitride target are simultaneously opened, direct-current sputtering power of 50-400W is used for the silver target, radio-frequency sputtering power of 80-400W is used for the aluminum nitride target, a thin film is jointly sputtered and deposited on a substrate, and the thickness of a silver film is controlled by controlling the sputtering time (the thickness range of the silver film is 10-100 nm).
Step 5: and after the film coating process is finished, keeping the gas condition unchanged, and after waiting for at least ten minutes, inflating the vacuum cavity, and taking out the prepared silver film sample.
Step 6: and (3) measuring the real part and the imaginary part of the dielectric constants of the silver film samples with the same thickness and prepared under the sputtering power of different silver targets and aluminum nitride targets under different incident light wavelengths, and drawing to obtain a series of dielectric constant-wavelength curves of the silver films prepared under different preparation conditions, wherein the curves are equivalent to the steps S1 and S2.
Step 7: based on the dielectric constant-wavelength curve, the sputtering power and the nitrogen content of the growth gas of the silver target material and the aluminum nitride target material for preparing the target silver film are selected and the silver film is prepared, so that the composite dielectric constant of the silver film is finally and effectively controllable, which is equivalent to the steps S3 and S4. For example, at 365nm incident wavelength, the real part regulation range of the silver film is-2.0 to-2.6, and the imaginary part regulation range is 0.4 to 1.0.
And the silver film prepared by the method has lower surface roughness. The silver films prepared in this example all had a root mean square roughness RMS of less than 0.6nm in the 1*1 μm range, whereas silver films without aluminum nitride doping typically had a root mean square roughness RMS of greater than 1.2nm in the 1*1 μm range.
According to the above steps 1 to 7, 3 specific examples are provided below.
Example 1:
according to the design of a micro-nano device, a silver film needs to be grown on a silicon wafer as a bottom electrode layer. In order to ensure the reliability and uniformity of the device, the surface of the silver film is required to have high flatness, and the root mean square roughness RMS of the surface is required to be less than 0.5nm.
As shown in fig. 2, a silver film with extremely low surface roughness was prepared by co-sputtering a pure silver target and an aluminum nitride target using a silicon wafer as a substrate by a magnetron sputtering method. First, the vacuum chamber for film growth was evacuated to 10 -6 Background vacuum in Torr. Introducing 20% Ar+80% N 2 The (volume ratio) of the mixture, the vacuum valve was adjusted to maintain the chamber pressure at 3.0mTorr. Simultaneously opening the baffle plates of the silver target and the aluminum nitride target, using a direct current power supply with the power of 50W for the silver target, using a radio frequency power supply with the power of 100W for the aluminum nitride target, and starting the power supply to enable the two targets to be started simultaneously. Before sputtering coating, pre-sputtering the silver target and the aluminum nitride target for more than 30s, removing impurities on the surface of the target, and controlling the thickness of the film by controlling the sputtering time to finish the preparation.
After taking out the sample, measuring the RMS of the surface of the sample by an atomic force microscope, and measuring the RMS to be 0.35nm, as shown in fig. 3, wherein a graph a in fig. 3 is an atomic force microscope image of the silver film prepared in the embodiment in the range of 1*1 μm, and the surface root mean square roughness rms= 0.3433nm; fig. 3 b shows an atomic force microscope image of a silver film prepared by sputtering a pure silver target in the 1*1 μm range, with a surface root mean square roughness rms= 1.2305nm. Therefore, the surface roughness of the silver film prepared by the method of this example meets the design requirements.
Example 2:
in order to meet different technical requirements, the sputtering power of the silver target and the aluminum nitride target during co-sputtering is regulated, a series of silver films are prepared by the method, dielectric constant-wavelength functions of the silver films are prepared by using ellipsometry to represent different process parameters, as shown in fig. 4, the left graph in fig. 4 shows a change curve of a real part of the dielectric constant with the wavelength of incident light, and the right graph in fig. 4 shows a change curve of an imaginary part of the dielectric constant with the wavelength of incident light. It can be seen that the real part and the imaginary part of the dielectric constant of the aluminum nitride doped silver film are changed compared with the silver film sputtered by a pure silver target. Taking the dielectric constant at 365nm as an example, the real part and the imaginary part of the dielectric constant of the silver film under different process parameters can be obtained, the real part regulation and control range of the silver film is-2.0 to-2.6, and the imaginary part regulation and control range is 0.4 to 1.0, so as to be used for different technical requirements, as shown in figure 5.
Example 3:
in a certain super diffraction imaging photoetching technology, in order to improve the imaging quality of nano patterns, the design needs that the RMS of a silver film is smaller than 0.5nm, meanwhile, the real part of the dielectric constant at 365nm incidence wavelength is about-2.2, and the real part of the dielectric constant of the silver film prepared by pure silver target sputtering is-2.9, so that the roughness and the dielectric constant of the silver film need to be regulated and controlled.
To meet the technical demand, the silver film RMS prepared by the method can meet the demand; the dielectric constant of the silver film was controlled according to the dielectric constant curve (as shown in fig. 5) of a series of silver films prepared by the method in example 2, and it was found that the real part of the dielectric constant of the silver film prepared by using the sputtering power of 150W for the aluminum nitride target was close to the demand.
Thus, the desired silver film can be prepared by the methods of the present disclosure using a silicon wafer as a substrate and selecting appropriate process parameters (see example 1 for specific preparation procedures).
After the preparation, the surface morphology and dielectric constant of the silver film prepared by atomic force microscope and ellipsometer characterization. The test shows that the RMS of the prepared silver film is 0.38nm, the real part of the dielectric constant at 365nm incidence wavelength is-2.22, and the design requirement is met.
Further, photoresist is spin-coated on the surface of the prepared silver film, super-diffraction imaging exposure is carried out, and compared with the imaging effect of the silver film prepared by the traditional method, as shown in fig. 6, the a, b and c diagrams in fig. 6 are the photoetching exposure imaging effect (the characteristic dimensions are 64nm,44nm and 32nm respectively) when the silver film prepared by the single-target sputtering process in the traditional method is used as a super-diffraction layer; fig. 6 shows the effects of photolithographic exposure imaging (feature sizes 64nm,44nm and 32nm, respectively) of silver films prepared by the method of the present disclosure as super-diffraction layers.
As can be seen, the silver film prepared by the method of the present disclosure as a super diffraction layer has superior imaging quality (pattern contrast, line edge roughness, line width uniformity, etc.) to that of the silver film prepared by the conventional method. According to the preparation method disclosed by the invention, the target silver film can be prepared by selecting proper growth conditions according to technical requirements, so that the preparation of the silver film with adjustable dielectric constant is realized, and the optical performance of the silver film serving as the super diffraction layer is effectively optimized.
In conclusion, the silver film preparation method disclosed by the invention is based on the mature magnetron sputtering equipment, has low reconstruction and consumable cost and simple operation, effectively regulates and controls the composite dielectric constant of the silver film, overcomes the technical difficulty of the silver film in practical application, effectively reduces the surface roughness of the silver film, and greatly expands the application range of the silver film in photoelectric devices.
While the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and that any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the present disclosure are intended to be included within the scope of the present disclosure.
Claims (9)
1. A method for preparing a silver film with low roughness and controllable dielectric constant, comprising the steps of:
s1, introducing mixed gas of argon and nitrogen into a vacuum cavity, adjusting sputtering power of a silver target and aluminum nitride target, and jointly performing sputtering deposition to prepare a plurality of silver films under different sputtering powers;
s2, obtaining a plurality of dielectric constant-wavelength curves of the silver films;
s3, determining the first sputtering power of the silver target and the second sputtering power of the aluminum nitride target according to the dielectric constant-wavelength curves based on the target dielectric constant of the target silver film under the specific wavelength, wherein the method comprises the following steps: determining a first dielectric constant-wavelength curve corresponding to the specific wavelength and the target dielectric constant in the multiple dielectric constant-wavelength curves according to the target dielectric constant of the target silver film under the specific wavelength; determining a first sputtering power of the silver target and a second sputtering power of an aluminum nitride target according to the first dielectric constant-wavelength curve;
and S4, introducing the mixed gas of the argon and the nitrogen into the vacuum cavity, using the first sputtering power for the silver target material and the second sputtering power for the aluminum nitride target material, and depositing to prepare the low-roughness silver film under the target dielectric constant after aluminum nitride doping.
2. The method for preparing a silver film with controllable low roughness and dielectric constant according to claim 1, wherein the step of introducing a mixed gas of argon and nitrogen into the vacuum chamber in S1 comprises:
vacuumizing the cavity to form a vacuum cavity;
and introducing mixed gas of argon and nitrogen into the vacuum cavity, wherein the regulating range of the working cavity pressure is 1.0 mTorr-5.0 mTorr.
3. The method for preparing a silver film with low roughness and controllable dielectric constant according to claim 2, wherein the volume ratio of nitrogen in the mixed gas of argon and nitrogen is 20% -100%.
4. The method for preparing a silver film with controllable low roughness and dielectric constant according to claim 1, wherein the step S1 of adjusting the sputtering power of the silver target and the aluminum nitride target, the step of preparing a plurality of silver films with different sputtering powers by co-sputtering deposition comprises the steps of:
pre-sputtering the silver target and the aluminum nitride target to remove surface impurities;
sputtering the silver target material by using direct current sputtering, and sputtering the aluminum nitride target material by using radio frequency sputtering, and jointly sputtering and depositing a silver film on a substrate;
and adjusting the power of the direct current sputtering and the power of the radio frequency sputtering, and depositing and preparing a plurality of silver films under different sputtering powers.
5. The method for producing a silver film having a low roughness and a controllable dielectric constant as claimed in claim 4, wherein the thicknesses of the plurality of silver films are equal, and the thickness of the silver film ranges from 10nm to 100nm.
6. The method for preparing a silver film with low roughness and controllable dielectric constant as claimed in claim 4, wherein the power of the direct current sputtering is 50W to 400W and the power of the radio frequency sputtering is 80W to 400W.
7. The method for producing a low-roughness and controllable-dielectric-constant silver film according to claim 4, wherein the surface material of said substrate comprises Si, siO 2 One of Ge, siBARC, znO.
8. The method for producing a low roughness and controllable dielectric constant silver film as claimed in claim 1, wherein said S2 comprises:
collecting dielectric constant data of each silver film at different wavelengths by using an ellipsometer;
and fitting the dielectric constant data at different wavelengths to obtain a dielectric constant-wavelength curve of each silver film.
9. The silver film with controllable low roughness and dielectric constant is characterized in that the silver film is prepared by the preparation method of the silver film with controllable low roughness and dielectric constant according to any one of claims 1 to 8.
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