Method for producing metal-containing film blank

Abstract

The invention relates to a method for producing a (Omega) metal-containing film blank (1), wherein the method comprises the following steps: applying (E 1) a bottom layer on a substrate; vapor deposition (E < 2 >) of a metal to form a multi-layer composite structure comprising a metal film; placing (S1) the structure (10) in the liquid (M1); and breaking (S2) the sublayer (101). According to the invention, the underlayer (101) comprises copper. The film (100) contains a noble metal. Furthermore, the invention relates to a coating method (psi) for coating said blank (1) to a target carrier (2), and to the use of a target carrier.

Description

Technical Field

[0001] The present invention relates to the field of optoelectronics, and in particular to a method for preparing a thin metal film on a target carrier, for example on a (light) transmissive target carrier such as glass. Background Art

[0002] The term "thin" in the context of metal films means that the thickness of such films is usually no more than 0.5 micrometers, hereinafter referred to as μm. Summary of the invention

[0003] According to a first aspect of the present invention, the present invention relates to a method for preparing a metal-containing film blank suitable for application to a target carrier. This preparation method comprises:

[0004] a stage of forming a multilayer composite structure including a metal film, and

[0005] • A stage of breaking the multilayer composite structure to produce a metal-containing film blank.

[0006] Therefore, the stage of destroying the multilayer composite structure is carried out after the stage of forming the multilayer composite structure. Under these conditions, the stage of forming the multilayer composite structure includes further steps, which are aimed at:

[0007] Applying a primer layer on the substrate to form a base material layer,

[0008] Depositing a metal on the substrate layer to form a multi-layer composite structure comprising a metal film bonded to the substrate layer.

[0009] Therefore, the stage of destroying such a multilayer composite structure includes further steps aimed at:

[0010] placing a portion of the multilayer composite structure in a first liquid medium,

[0011] ·Destroy the bottom layer.

[0012] This preparation method is known and disclosed in the Russian Federation patent RU2329875C2. The disadvantage of this prior art method for preparing a metal film blank suitable for application to a target carrier is that its integrity (i.e., robustness) can only be achieved when the thickness of the metal film blank is greater than 30 nanometers (hereinafter referred to as -nm). This metal film thickness prevents visible light from passing through the film. Therefore, it is impossible to provide the required transmission capacity (in the optical band of the spectrum visible to the human eye) using the prior art method of RU2329875C2, which is unacceptable.

[0013] Attempts to use the prior art method of RU2329875C2 to prepare metal film blanks with a thickness of less than 30 nm result in the formation of a plurality of scattered metal islands (spots) of irregular thickness and shape, which are separated from each other. The latter do not have the expected smoothness, firmness and sufficient cohesion to form a continuous film-type coating with each other. In addition, such a plurality of scattered metal islands (spots) is characterized by insufficient current conductivity, which is unacceptable.

[0014] Based on this unique research, the main purpose of the present invention is to propose a method for preparing a metal film blank suitable for application to a target carrier, which method makes it possible to alleviate at least one of the above-mentioned disadvantages. In order to achieve this goal, the method for preparing a metal film blank corresponding to the general description given in the above introduction is essentially characterized in that the bottom layer contains copper. The metal film contains at least one metal from the following metal group: (a) gold; (b) silver; (c) platinum; (d) ruthenium; (e) rhodium; (f) palladium; (g) osmium; (h) iridium.

[0015] Due to the high adhesion between the above-mentioned metals (i.e. gold, silver, platinum, ruthenium, rhodium, palladium, osmium or iridium) and copper, it is possible to produce metal film blanks with a thickness of less than 30 nm and with sufficient smoothness, firmness and cohesion, which provide sufficient transmission capacity in the optical band of the spectrum visible to the human eye and have high (electrical) current conductivity. The synergistic effect of these two advantages, i.e. the simultaneous combination, expands the functionality of the method according to the invention for producing metal film blanks.

[0016] Preferably, the first liquid medium comprises an electrolyte. Under these conditions, the stage of destroying the multilayer composite structure also comprises a further step, the purpose of which is:

[0017] • Introducing a first electrode different from the multilayer composite structure into the first liquid medium.

[0018] forming an anode by connecting the first electrode to the positive terminal of an external DC power source,

[0019] forming a cathode by connecting the bottom layer to the negative electrode of the external DC power source, wherein the negative electrode is different from the positive electrode,

[0020] Establishing an electrolysis process in the first liquid medium between the cathode and the anode, generating electrolytic bubbles inside the first liquid medium along the edge of the bottom layer in contact with the first liquid medium,

[0021] maintaining the electrolysis process in a first liquid medium between the cathode and the anode to mechanically tear the bottom layer from the substrate by the electrolytic bubbles,

[0022] Immersing the multilayer composite structure in a first liquid medium while the bottom layer is separated from the substrate, until the bottom layer is completely separated from the substrate, forming a sandwich structure comprising the bottom layer and the metal film bonded together.

[0023] Due to the advantageous properties, electrolytic bubbles are generated in the first liquid medium along the edge of the bottom layer in contact with the first liquid medium. The generated electrolytic bubbles come into contact with the multilayer composite structure and penetrate between the substrate and the sandwich structure consisting of the bottom layer and the metal film. As the volume expands, the electrolytic bubbles gradually tear the sandwich structure from the substrate. In addition, the electrolytic bubbles help (surface tension acting on the sandwich structure) to maintain the positive buoyancy of the sandwich structure on the surface of the first liquid medium (once it is separated from the substrate). The process of tearing the sandwich structure and the substrate forms cracks, i.e., defects in the multilayer composite structure, representing areas where the interatomic bonds are completely broken (crack planes) and where the interatomic bonds are partially broken (crack tips). The crack face separation surface is the crack front. As the crack propagation progresses (i.e., the sandwich structure is separated from the substrate), the first liquid medium (i.e., the electrolyte) penetrates (flows) toward the crack tip, promoting the electrolysis process, thereby generating additional electrolytic bubbles near the crack tip. The additional electrolytic bubbles further open the crack planes that contribute to the crack growth until the sandwich structure is completely separated from the substrate. Therefore, the influence of the electrolytic bubbles on the sandwich structure will not cause mechanical damage to the sandwich structure, such as cracking, warping, agglomeration, and adhesion. Therefore, further operation of the sandwich structure is simplified, which helps to expand the function of the metal film blank according to the present invention.

[0024] Therefore, it is critical that the cathode is formed exclusively on the bottom layer of the multilayer composite structure because the electrolytic bubbles required to tear the bottom layer from the substrate must be formed exclusively on the bottom layer.

[0025] Preferably, the electrolyte consists of a potassium chloride solution having a molar concentration in the range of 0.05 mol / L to 7.6 mol / L.

[0026] This specific choice of potassium chloride solution as electrolyte is due to its availability, ease of preparation and low toxicity to operators and the environment. Therefore, the method according to the invention can be suitable for commercial preparation of metal-containing membrane blanks on the basis of large-scale preparation, including in the case of artificially limiting the range of available chemical reagents. The selective selection of the molar concentration of potassium chloride solution in the range of 0.05 mol / l to 7.6 mol / l makes it possible to generate the required amount of electrolytic bubbles during the electrolysis process, which is sufficient to separate the substrate from the sandwich structure without causing mechanical damage to the sandwich structure. This helps to reduce the proportion of defective products in large-scale preparation.

[0027] According to a first embodiment of the manufacturing method of the present invention, the step of damaging the bottom layer includes a step aimed at replacing the first liquid medium with a second liquid medium chemically aggressive to the bottom layer to chemically etch the bottom layer.

[0028] Due to this property, the metal film can be released from the bottom layer by chemically destroying the bottom layer. Therefore, by increasing or decreasing the speed of replacing the first liquid medium with the second liquid medium, the etching rate can be finely adjusted. This helps to reduce the percentage of defective products in large-scale production.

[0029] According to a second embodiment of the manufacturing method of the present invention, which is an alternative to the above-mentioned first embodiment: the step of destroying the bottom layer includes a step, the purpose of which is to transfer the sandwich structure comprising the bottom layer and the metal film bonded together from the first liquid medium to a second liquid medium that is chemically corrosive to the bottom layer, so as to chemically etch the bottom layer.

[0030] In this second embodiment of the manufacturing method according to the invention, the chemical etching process is carried out faster than in the first embodiment described above, because the sandwich structure is exposed to the chemically aggressive second liquid medium instantaneously (i.e., as soon as the sandwich structure is transferred into the second liquid medium). Therefore, the method according to the invention can be adapted for commercial production of metal-containing membrane blanks on a large-scale production basis.

[0031] Preferably, the second liquid medium consists of one of the following solutions: (a) ammonium persulfate solution; (b) sodium persulfate solution; (c) hydrogen peroxide and sodium persulfate solution; (d) sulfuric acid solution; (e) sulfuric acid and hydrogen peroxide solution.

[0032] This specific choice of the above solutions as second liquid medium is explained by their availability and ease of preparation.Thus, the method according to the invention can be adapted for commercial preparation of metal-containing membrane blanks on a large-scale production basis, including in cases where the range of available chemical reagents is artificially limited.

[0033] According to a third embodiment of the preparation method of the present invention, the stage of destroying the multilayer composite structure may further include a step aimed at replacing the second liquid medium with distilled water in order to remove the chemical reaction products.

[0034] Flushing with distilled water reliably removes any residual salts of the first liquid medium and / or residual salts of the second liquid medium, which could adversely affect the integrity of the metal film if they accidentally crystallize. Thus, by increasing or decreasing the rate of replacement of the second liquid medium with distilled water, the removal rate of the chemical reaction products can be finely adjusted. This helps to reduce the percentage of defective products in large-scale preparations.

[0035] According to a fourth embodiment of the preparation method of the present invention, which is an alternative to the third embodiment described above, the stage of destroying the multilayer composite structure also includes a further step aimed at transferring the metal film from the second liquid medium into distilled water to remove the chemical reaction products.

[0036] Flushing with distilled water can reliably remove any residual salts of the first liquid medium and / or residual salts of the second liquid medium, which, if they accidentally crystallize, may adversely affect the integrity of the metal film. In the fourth embodiment of the preparation method according to the present invention, since the metal film is instantly transferred to distilled water, the process of removing the chemical reaction products is faster than in the third embodiment described above. Therefore, the method according to the present invention can be suitable for commercial preparation of metal-containing film blanks on a large-scale production basis.

[0037] Preferably, the stage of destroying the multilayer composite structure also comprises a further step aimed at achieving the flotation of the sandwich structure on the surface of the first liquid medium after the bottom layer has been completely separated from the substrate.

[0038] During the replacement of the first liquid medium with the second liquid medium, flotation on the surface of the first liquid medium additionally protects the sandwich structure (after its bottom layer is completely separated from the substrate) from mechanical damage, such as cracking, warping, agglomeration, adhesion. Therefore, the method according to the present invention can be suitable for commercial preparation of metal-containing membrane blanks on a large-scale production basis.

[0039] Preferably, the stage of destroying the multilayer composite structure also comprises a step aimed at achieving flotation of the sandwich structure on the surface of the second liquid medium during chemical etching of the bottom layer.

[0040] During appropriate chemical etching of the bottom layer and during the subsequent replacement of the second liquid medium with distilled water, flotation on the surface of the second liquid medium additionally protects the sandwich structure (after its bottom layer is completely separated from the substrate) from mechanical damage, such as cracking, warping, agglomeration, adhesion. Therefore, the method according to the present invention can be suitable for commercial production of metal-containing thin film blanks on a large-scale production basis.

[0041] Preferably, the stage of destroying the multilayer composite structure also comprises a further step aimed at achieving flotation of the metal film on the surface of distilled water during the removal of the chemical reaction products.

[0042] Floatation on the distilled water surface protects the metal membrane from mechanical damage, such as cracking, warping, agglomeration, and adhesion, during the removal of chemical reaction products.

[0043] Preferably, the substrate comprises one of the following materials: (a) a single crystal silicon wafer; (b) a single crystal silicon wafer having a graphene layer pre-applied thereon; (c) a single crystal silicon wafer containing silicon oxide; (d) a single crystal silicon wafer containing silicon oxide having a graphene layer pre-coated thereon; (e) glass; (f) sapphire; (g) copper foil; (h) poly(4,4'-oxydiphenylene-tetramethyleneimine); (i) polyethylene terephthalate; (j) polyether; (k) polypropylene; (l) polyethylene; (m) polyvinyl chloride; (n) polystyrene; (o) polytetrafluoroethylene; (p) polymethyl methacrylate.

[0044] Due to the wide selection of substrate materials, the method according to the present invention can be adapted for commercial production of metal-containing thin film blanks on a large-scale production basis, including in cases where the range of available materials is artificially limited.

[0045] Preferably, the first thickness of the bottom layer is in a first range of 20 nanometers to 10000 nanometers. Under these conditions, the second thickness of the metal film is in a second range of 0.5 nanometers to 30 nanometers.

[0046] Due to these advantageous features, the method according to the invention can be adapted for the commercial production of metal-containing membrane blanks on a large-scale production basis, wherein each production stage is limited in terms of time and percentage of defective products.

[0047] Preferably, the multilayer composite structure is immersed in the first liquid medium while the bottom layer is separated from the substrate, along a guide line having an angle in a third range of 5° to 15° relative to the gravity vector.

[0048] Due to this advantageous property, the separation of the bottom layer from the substrate is carried out in the most efficient manner, and therefore the method according to the invention can be adapted for the commercial preparation of metal-containing film blanks on a large-scale production basis. In addition, the angles from 5° to 15° relative to the gravity vector are easy for the operator to monitor, which makes the operator's work easier and minimizes fatigue (which is particularly important when working at night).

[0049] Preferably, the stage of forming the multilayer composite structure also comprises a further step aimed at coating the metal film with a polymer protective layer.

[0050] Due to this advantageous property, the rigidity of the sandwich structure comprising the bottom layer and the metal film can be increased. This can also protect the sandwich structure (after its bottom layer is completely separated from the substrate) from mechanical damage such as cracking, warping, agglomeration, and adhesion during operator handling.

[0051] After the chemical etching of the bottom layer is completed, the polymer protective layer also increases the rigidity of the metal film itself. This can also protect the metal film from mechanical damage such as cracking, warping, agglomeration, and sticking during operator handling.

[0052] The method according to the invention is therefore suitable for the commercial production of metal-containing film blanks on a large-scale production basis, where each production stage is limited in terms of time, percentage of defective products, and should be understood regardless of the qualifications of the operator.

[0053] Preferably, the polymer comprises one of the following materials: (a) polymethyl methacrylate; (b) polydimethylsiloxane, (c) polycarbonate, (d) polylactic acid; (e) polyphthalamide; (f) bisphenol A.

[0054] The materials for the polymeric protective layer are selected from the above list because of their availability and ease of preparation. Thus, the method according to the present invention can be adapted for commercial preparation of metal-containing membrane blanks on a large-scale production basis, including in cases where the range of available polymers is artificially limited.

[0055] According to a second aspect of the present invention, the present invention relates to a method for coating a target carrier with a metal-containing film blank prepared according to the above preparation method. Therefore, the coating method comprises a further step, the purpose of which is to:

[0056] Transferring the metal-containing film blank to the target carrier,

[0057] After the metal-containing film blank is transferred to the target carrier, the metal-containing film blank is subjected to a dehumidification treatment,

[0058] Due to these advantageous properties, it is possible to produce target supports which are coated with homogeneous metal films, wherein the films are simultaneously transparent (in the visible spectrum of radiation), electrically conductive and corrosion-resistant.

[0059] Preferably, the method for coating a target carrier with a metal-containing film blank prepared according to the above preparation method comprises a stage of forming a multilayer composite structure, which stage also comprises a further step aimed at coating the metal film with a polymer protective layer. Under these conditions, the coating method comprises a further step aimed at:

[0060] Transferring the metal-containing film blank to the target carrier,

[0061] Removal of polymer protective layer,

[0062] Dehumidification of the metal-containing film blank once it has been transferred to the target carrier,

[0063] The presence of the polymer protective layer on the metal film increases the rigidity of the film, making it easier to transfer the film to a target carrier without causing mechanical damage. Therefore, the method according to the invention can be adapted to the commercial preparation of metal-containing film blanks on a large-scale production basis, regardless of the qualifications of the operator. The subsequent removal of the polymer protective layer makes it possible to prepare a target carrier coated with a uniform metal film, wherein the film is simultaneously transparent (in the visible spectrum of radiation), conductive and corrosion-resistant.

[0064] According to its third aspect, the present invention relates to the use of a target carrier coated with a metal-containing film blank according to the above-mentioned coating method as one of the following products: (a) a transparent electrode; (b) a thin film solar cell; (c) a photodetector; (d) a light emitting diode; (e) a contact lens for the eye; (f) a flat screen; (g) a flexible screen; (h) a touch screen; (i) an electrochromic device; (j) a gas sensor; (k) a chemical sensor; (l) a biosensor; (m) a thin film type flexible nanoelectronic device.

[0065] This makes it possible to use the target carrier coated with the metal-containing thin film blank in various fields, which in turn expands the functionality of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Other features and advantages of the present invention will become apparent from the following description, given by way of illustration and not limitation, with reference to the accompanying drawings, in which:

[0067] · Figure 1 A method for coating a target support with a metal-containing film blank according to the present invention is schematically represented;

[0068] · Figure 2 shows a simplified cross-sectional side view of an exemplary multilayer composite structure including a substrate, a base layer, a metal film, and a polymer protective layer;

[0069] · Figure 3 a schematic simplified cross-sectional side view showing the step of immersing the multilayer composite structure in a first liquid medium;

[0070] · Figure 4 shows a simplified cross-sectional side view of the step of separating the bottom layer from the substrate under the influence of electrolytic bubbles generated by electrolysis in the first liquid medium;

[0071] · Figure 5 A schematic simplified cross-sectional side view showing the step of floating a sandwich structure comprising a bottom layer, a metal film and a polymer protective layer on a surface of a second liquid medium during chemical etching of the bottom layer;

[0072] · Figure 6shows a simplified cross-sectional side view of the flotation step of a metal membrane with a polymer protective layer on a distilled water surface during the removal of chemical reaction products;

[0073] · Figure 7 showing a simplified cross-sectional side view of a target support of a metal film coated with a polymer protective layer before removal of the polymer protective layer;

[0074] · Figure 8 showing a simplified cross-sectional side view of a target support having a metal film coated with a polymer protective layer after removal of the polymer protective layer;

[0075] · Fig. 9 A top view of a section of a metal film (coating a target carrier) taken using an electron microscope is shown. DETAILED DESCRIPTION

[0076] like Figure 1-9 As shown, according to its first aspect, the present invention relates to a method for preparing a metal-containing film blank suitable for application to a target carrier 2. The method for preparing Ω comprises:

[0077] a stage of forming a multilayer composite structure 10 comprising a metal film 100, and

[0078] The stage of destroying ω2 the multilayer composite structure 10 to prepare a metal film-containing blank 1.

[0079] Therefore, the stage of destroying the ω2 multilayer composite structure 10 follows the stage of forming the ω1 multilayer composite structure 10 .

[0080] like Figure 1 As shown, a multilayer composite structure 10 ( Figure 2 ) stage includes further steps aimed at:

[0081] Applying the bottom layer 101 to the substrate 102 to form the base material layer P,

[0082] Depositing E2 metal on the substrate layer P to form a multilayer composite structure 10 comprising a metal film 100 bonded to the substrate layer P.

[0083] In addition, if Figure 1 As shown, the stage of destroying the ω2 multilayer composite structure 10 includes further steps, the purpose of which is to:

[0084] · Place a portion of the multilayer composite structure 10 in the first liquid medium M1 ( Figure 3-4 ),

[0085] ·Destroy S2 bottom 101 ( Figure 4-5 ).

[0086] According to the invention, the bottom layer 101 comprises copper. Under these conditions, the metal film 100 comprises at least one metal from the following metal group:

[0087] (a) gold; (b) silver; (c) a platinum group metal (i.e. platinum, ruthenium, rhodium, palladium, osmium or iridium).

[0088] Preferably, the first liquid medium M1 comprises an electrolyte. Under these conditions, Figure 1 As shown, the stage of destroying the ω2 multilayer composite structure 10 also includes further steps, the purpose of which is to:

[0089] S3 is introduced into the first liquid medium M1, that is, different from the first electrode 3 ( Figure 3 ),

[0090] By connecting the first electrode 3 to the positive electrode I of the external DC power source I A , forming S4 anode ( Figure 3 ),

[0091] By connecting the bottom layer 101 to the negative electrode I of the external DC power source I K , forming S5 cathode, where the negative electrode I K Different from positive electrode I A ( Figure 3 ),

[0092] · Establishing S6 electrolysis process in the first liquid medium M1 between the cathode and the anode, wherein electrolytic bubbles π are generated in the first liquid medium M1 along the edge 1010 of the bottom layer 101 in contact with the first liquid medium M2 ( Figure 3-4 ),

[0093] The electrolysis process is maintained in the first liquid medium M1 between the cathode and the anode to mechanically tear the bottom layer 101 away from the substrate 102 by the electrolytic bubbles π ( Figure 4 ),

[0094] The multilayer composite structure 10 is immersed in the first liquid medium M1 in step S7, and the bottom layer 101 is separated from the substrate 102 until the bottom layer 101 is completely separated from the substrate 102, thereby forming a sandwich structure Z ( Figure 4 ).

[0095] Preferably, the electrolyte may be composed of a molar concentration C M Composition of potassium chloride solution in the range of 0.05 mol / L to 7.6 mol / L:

[0096] 0.05mol / l≤C M ≤7.60mol / l.

[0097] According to the first embodiment of the preparation method of the present invention ( Figure 1 ), the step S2 of destroying the bottom layer 101 includes a further step, which aims to replace S9 the first liquid medium M1 with a second liquid medium M2 that is chemically corrosive to the bottom layer 101 to chemically etch the bottom layer 101.

[0098] According to the second embodiment of the production method of the present invention ( Figure 1 ), which is an alternative to the first embodiment described above: the step S2 of destroying the bottom layer 101 comprises a further step, the purpose of which is to transfer the sandwich structure Z comprising the bottom layer 101 and the metal film 100 bonded together from the first liquid medium M1 to S 10 The bottom layer 101 is then chemically etched into a second liquid medium M2 that is chemically corrosive to the bottom layer 101 .

[0099] Preferably, the second liquid medium M2 consists of one of the following solutions: (a) ammonium persulfate solution; (b) sodium persulfate solution; (c) hydrogen peroxide and sodium persulfate solution; (d) sulfuric acid solution; (e) sulfuric acid and hydrogen peroxide solution.

[0100] According to the third embodiment of the preparation method of the present invention ( Figure 1 ), the stage of destroying the ω2 multilayer composite structure 10 also includes a further step, the purpose of which is to replace S with distilled water W 11 The second liquid medium M2 is used to remove chemical reaction products.

[0101] According to a fourth embodiment of the preparation method of the present invention, which is an alternative to the third embodiment described above, the stage of destroying the ω2 multilayer composite structure 10 also includes a further step, which is aimed at transferring the metal film 100 from the second liquid medium M2 to 12 Another step to remove chemical reaction products is to distill water W.

[0102] like Figure 1 As shown, the stage of destroying the ω2 multilayer composite structure 10 also includes a further step, which is aimed at achieving S after the bottom layer 101 is completely separated from the substrate 102. 13 Floatation of the sandwich structure Z on the surface N1 of the first liquid medium M1.

[0103] like Figure 1 As shown, the stage of destroying the ω2 multilayer composite structure 10 also includes a further step, which is aimed at achieving S during the chemical etching of the bottom layer 101. 14 Flotation of the sandwich structure Z on the surface N2 of the second liquid medium M2 ( Figure 5 ).

[0104] like Figure 1As shown, the stage of destroying the ω2 multilayer composite structure 10 also includes a further step, which is aimed at achieving the flotation S of the metal film 100 on the surface N3 of the distilled water W during the removal of the chemical reaction products. 15 ( Figure 6 ).

[0105] Preferably, the substrate 102 comprises one of the following materials:

[0106] (a) Single crystal silicon wafer;

[0107] (b) a single crystal silicon wafer on which a graphene layer has been previously applied;

[0108] (c) a single crystal silicon wafer containing silicon oxide;

[0109] (d) a single crystal silicon wafer containing silicon oxide, on which a graphene layer is pre-coated;

[0110] (e) glass; (f) sapphire; (g) copper foil;

[0111] (h) poly (4,4'-diphenyl oxide-pyromellitimide);

[0112] (i) polyethylene terephthalate; (j) polyether; (k) polypropylene;

[0113] (l) Polyethylene; (m) Polyvinyl chloride; (n) Polystyrene;

[0114] (o) Polytetrafluoroethylene; (p) Polymethyl methacrylate.

[0115] Preferably, the first thickness α of the bottom layer 101 is included in a first range of 20 nm to 10,000 nm: 20 nm ≤ α ≤ 10,000 nm ( Figure 2 Under these conditions, the second thickness β of the metal film 100 is within a second range of 0.5 nm to 30 nm: 0.5 nm ≤ β ≤ 30 nm ( Figure 2 ).

[0116] like Figure 3-4 As shown, the multilayer composite structure 10 is immersed S8 in the first liquid medium M1, and separation of the bottom layer 101 from the substrate 102 occurs along a reference line that forms an angle μ within a third range of 5° to 15° relative to the gravity vector G: 5°≤μ≤15°.

[0117] like Figure 1 As shown, the stage of forming the multilayer composite structure 10 also includes a further step, which is aimed at coating the E3 metal film 100 ( Figure 2 ).

[0118] Preferably, the polymer comprises one of the following materials: (a) polymethyl methacrylate; (b) polydimethylsiloxane, (c) polycarbonate, (d) polylactic acid; (e) polyphthalamide; (f) bisphenol A.

[0119] like Figure 1 , 8 According to its second aspect, the present invention relates to a method Ψ for coating a target carrier 2, the target carrier 2 having a metal-containing film blank 1 prepared according to the above-mentioned preparation method Ω. The coating method Ψ comprises a further step, the purpose of which is:

[0120] · Transferring the metal-containing film blank 1 to the target carrier 2 by Φ1,

[0121] After the metal-containing film blank 1 is transferred Φ1 onto the target carrier 2, the metal-containing film blank 1 is dehumidified Φ2.

[0122] like Figure 1 , 7 -9, according to its third aspect, the present invention relates to a method for coating a Ψ target carrier 2, the target carrier 2 having a metal-containing film blank 1 prepared according to the above-mentioned preparation method of Ω, wherein the stage of forming a multilayer composite structure 10 also includes another step, the purpose of which is to coat the E3 metal film 100 ( Figure 2 ).

[0123] Preferably, the polymer comprises one of the following materials: (a) polymethyl methacrylate; (b) polydimethylsiloxane, (c) polycarbonate, (d) polylactic acid; (e) polyphthalamide; (f) bisphenol A.

[0124] Under these conditions, the coating method Ψ comprises further steps, the purpose of which is:

[0125] ·Transfer Φ1 of the metal-containing film blank 1 to the target carrier 2 ( Figure 7 ),

[0126] ·Remove Φ 10 The polymer protective layer 103,

[0127] After the metal-containing film blank 1 is transferred to the target carrier 2, the metal-containing film blank 1 is subjected to Φ2 dehumidification ( Figure 8-9 ).

[0128] According to its fourth aspect, the present invention relates to a film blank 1 (coated with a metal-containing film according to the above coating method) Figure 8 ) as one of the following products:

[0129] (a) Transparent electrode; (b) Thin film solar cell; (c) Photodetector; (d) Light emitting diode; (e) Contact lens for eyes; (f) Flat screen; (g) Flexible screen; (h) Touch screen; (i) Electrochromic device; (j) Gas sensor; (k) Chemical sensor; (l) Biosensor; (m) Thin film flexible nanoelectronic device.

[0130] Therefore, the technical effect of the present invention is to prepare a thin (i.e., less than 0.5 micrometers in thickness, typically tens of nanometers) metal film, which contains at least one metal from the following metal group: (a) gold; (b) silver; (c) platinum group metal (i.e., platinum, ruthenium, rhodium, palladium, osmium or iridium), and at the same time:

[0131] Smooth, that is, uniform thickness, without warping, agglomeration, adhesion and other mechanical damage,

[0132] Strong and cohesive, i.e. free from mechanical failure.

[0133] Under these conditions, the metal film is transparent in the optical band of the spectrum visible to the human eye while carrying an electric current. In addition, the metal film is suitable for transfer to a target support by selecting a copper-soluble layer having high adhesion to metals from the following group of metals as the underlying material: (a) gold; (b) silver; (c) platinum group metals (i.e., platinum, ruthenium, rhodium, palladium, osmium or iridium).

[0134] Example 1. Coating a target carrier with a metal film made from a metal-containing film blank formed by breaking a multilayer composite structure on a substrate consisting of a single-crystal silicon wafer.

[0135] For the substrate (i.e., substrate layer), a single crystal silicon wafer for microelectronics was selected and manufactured according to the ET0.035.206 TUs specification. Then, on this substrate, a multilayer composite structure was formed. To this end, a copper bottom layer with a film thickness in the range of 0.1 micron to 0.5 micron was first applied to the substrate using an electron beam evaporation technique. Then, a gold film with a thickness in the range of 3 nanometers to 10 nanometers was precipitated (deposited) onto the copper bottom layer using the same electron beam evaporation technique. Afterwards, the gold film was coated with a protective layer of polymethyl methacrylate polymer using a centrifugal process. Therefore, a multilayer composite structure has been prepared.

[0136] Potassium chloride salt is then dissolved in water to prepare an electrolyte having a molar concentration ranging from 0.5 moles to 2.0 moles per liter.

[0137] The anode is introduced into the electrolyte. The multilayer composite structure is also immersed in the electrolyte: under these conditions, its bottom layer of copper forms the cathode.

[0138] Once a voltage is applied to the anode and cathode, an electrochemical reaction of electrolysis is observed in the electrolyte, resulting in the generation of electrolytic gas (hydrogen) bubbles along the edges of the underlying copper layer. These electrolytic gas (hydrogen) bubbles gradually penetrate between the substrate and the underlying copper layer, resulting in mechanical tearing of the underlying copper layer from the substrate. As a result, a sandwich structure consisting of the underlying copper layer, the gold film and the polymethyl methacrylate protective layer is formed, wherein the sandwich structure is floating, i.e., maintained on the electrolyte surface by surface tension and Archimedean forces, which act on the hydrogen bubbles generated during the electrolysis process.

[0139] To remove the underlying copper layer, the sandwich structure was moved from the electrolyte surface to the surface of an aqueous solution of ammonium persulfate with a molar concentration of 0.1 mol / l. After chemical etching, the underlying copper layer disappeared: on the surface of the aqueous solution of ammonium persulfate, only the gold film coated with a protective layer of polymethyl methacrylate remained floating.

[0140] In order to remove the products of the chemical reaction, the gold film coated with a polymethyl methacrylate protective layer was moved from the surface of the ammonium persulfate aqueous solution to the surface of distilled water.

[0141] After floating on a distilled water surface, the gold film coated with a polymethyl methacrylate protective layer is transferred to a target carrier. The polymethyl methacrylate protective layer is then removed using a suitable solvent, such as acetone, or isopropanol, or a mixture of acetone and isopropanol.

[0142] The prepared gold film can be additionally fixed on the target carrier by dehumidification.

[0143] After all these operations, the gold film:

[0144] Reliable coating of target carriers,

[0145] · Free from mechanical defects, damage, discontinuities, i.e. exhibiting the expected robustness and low roughness,

[0146] ·Transparent in the optical band of the spectrum visible to the human eye,

[0147] ·Transmitting current.

[0148] Example 2. Coating a target carrier with a metal film, which is made of a metal-containing film blank, which is formed by destroying a multilayer composite structure on a substrate consisting of a single-crystalline silicon wafer, on which a graphene layer has been previously applied.

[0149] First, a substrate is prepared. To this end, a graphene layer is applied on the surface of a single-crystal silicon wafer used in microelectronics, using standard laboratory techniques and manufactured in accordance with the ET0.035.206 TU specification. Then, on this substrate consisting of a single-crystal silicon wafer and a graphene layer previously applied thereon, a multilayer composite structure is formed. To this end, a copper base layer with a film thickness of 0.1 micrometer to 0.5 micrometer is applied continuously using the electron beam evaporation technique, and a gold film with a thickness of 3 nanometers to 10 nanometers is deposited on its surface using the same technique. The obtained structure is coated with a protective layer of a polymethyl methacrylate polymer using a centrifugal process.

[0150] The subsequent steps are similar to those described in Example 1 above.

[0151] The presence of graphene reduces the roughness of the "substrate / underlying copper layer" interface surface. This in turn makes it easier and faster for the underlying copper layer to tear from the substrate during electrolysis. In practice, this tearing occurs at a lower cathode voltage than the voltage required to achieve such tearing in Example 1. This helps to save energy and achieve more accurate current monitoring during electrolysis. In addition, the metal (gold) film in Example 2 also exhibits lower roughness than the metal (gold) film in Example 1. Due to the lower roughness, the metal (gold) film in Example 2 exhibits better (compared to the film of Example 1) robustness, transparency and conductivity. According to the applicant's estimate, this improvement in transparency and conductivity includes approximately (depending on the film thickness) +10% compared to the corresponding properties of the film of Example 1.

[0152] Example 3. Coating a target carrier with a metal film made from a metal-containing film blank formed by breaking a multilayer composite structure on a substrate consisting of copper foil.

[0153] Using electron beam evaporation technology, the following substances are sequentially applied to the surface of a substrate (i.e., substrate layer) composed of copper foil: a copper bottom layer with a thickness of 0.1 micrometer to 0.5 micrometer and a gold layer with a thickness of 3 nanometers to 10 nanometers. Afterwards, the gold layer is coated with a polymethyl methacrylate polymer using a centrifugal process. The subsequent steps are similar to those described in Example 1 above. The method of preparing a metal film according to Example 3 and using it to coat a target carrier is technically easier than the method described in Example 1 above.

Claims

1. A method for preparing (Ω) a metal-containing film blank (1) suitable for application to a target carrier (2), wherein the preparation (Ω) method comprises: a stage of forming (ω1) a multilayer composite structure (10) including a metal film (100), and a stage of destroying (ω2) the multilayer composite structure (10) after the formation (ω1) stage to produce a metal-containing film blank (1), Therefore, the stage of forming the (ω1) multilayer composite structure (10) comprises further steps, the purpose of which is: applying (E1) a primer layer (101) to a substrate (102) to form a base material layer (P), Depositing (E2) a metal on the substrate layer (P) to form a multilayer composite structure (10), the composite structure comprising a metal film (100) bonded to the substrate layer (P), Therefore, the stage of destroying (ω2) said multilayer composite structure (10) comprises further steps, the purpose of which is: placing (S1) a portion of the multilayer composite structure (10) in a first liquid medium (M1), Destroy (S2) the bottom layer (101), Characterized in that the bottom layer (101) comprises copper, and The metal film (100) comprises at least one metal selected from the following metal group: (a) gold; (b) silver; (c) platinum; (d) ruthenium; (e) rhodium; (f) palladium; (g) osmium; and (h) iridium.

2. The method for preparing a (Ω) metal-containing film blank (1) according to claim 1, characterized in that: The first liquid medium (M1) comprises an electrolyte, The stage of destroying (ω2) the multilayer composite structure (10) also comprises a further step, the purpose of which is: introducing (S3) a first electrode (3) different from the multilayer composite structure (10) into the first liquid medium (M1), By connecting the first electrode (3) to the positive electrode (I A ) to form (S4) anode, By connecting the bottom layer (101) to the negative electrode (I K ) forms (S5) a cathode, wherein the negative electrode (I K ) is different from the positive electrode (I A ), establishing (S6) an electrolysis process in the first liquid medium (M1) between the cathode and the anode, wherein electrolytic bubbles (π) are generated in the first liquid medium (M1) along the edge (1010) of the bottom layer (101) in contact with the first liquid medium (M1), maintaining (S7) the electrolysis process in a first liquid medium (M1) between the cathode and the anode to mechanically tear the bottom layer (101) from the substrate (102) by the electrolytic bubbles (π), While the bottom layer (101) is being separated from the substrate (102), the multilayer composite structure (10) is immersed (S8) in a first liquid medium (M1) until the bottom layer (101) is completely separated from the substrate (102) and a sandwich structure (Z) is formed comprising the bottom layer (101) and the metal film (100) bonded together.

3. The method for preparing a (Ω) metal-containing film blank (1) according to claim 2, characterized in that: The electrolyte consists of a potassium chloride solution having a molar concentration in the range of 0.05 mol / L to 7.6 mol / L.

4. The method for preparing a (Ω) metal-containing film blank (1) according to claim 3, characterized in that: The step of destroying (S2) the bottom layer (101) comprises a further step aimed at replacing (S9) the first liquid medium (M1) with a second liquid medium (M2) chemically aggressive to the bottom layer (101) in order to chemically etch the bottom layer (101).

5. The method for preparing a (Ω) metal-containing film blank (1) according to claim 4, characterized in that: The step of destroying (S2) the bottom layer (101) comprises a further step aimed at transferring (S3) the sandwich structure (Z) comprising said bottom layer (101) and the metal film (100) bonded together from the first liquid medium (M1) to the bottom layer (101). 10 ) into a second liquid medium (M2) that is chemically corrosive to the bottom layer (101) to chemically etch the bottom layer (101).

6. The method for preparing a (Ω) metal-containing film blank (1) according to claim 5, characterized in that: The second liquid medium (M2) consists of one of the following solutions: (a) ammonium persulfate solution; (b) sodium persulfate solution; (c) Hydrogen peroxide and sodium persulfate solutions; (d) sulfuric acid solution; (e) Sulfuric acid and hydrogen peroxide solutions.

7. The method for preparing a (Ω) metal-containing film blank (1) according to claim 6, characterized in that: The stage of destroying the (ω2) multilayer composite structure (10) also includes a further step, the purpose of which is to replace (S 11 ) a second liquid medium (M2) to remove the chemical reaction products.

8. The method for preparing a (Ω) metal-containing film blank (1) according to claim 6, characterized in that: The stage of destroying (ω2) the multilayer composite structure (10) also includes a further step aimed at transferring (S2) the metal film (100) from the second liquid medium (M2) to 12 ) into distilled water (W) to remove the chemical reaction products.

9. The method for preparing a (Ω) metal-containing film blank (1) according to claim 8, characterized in that: The stage of destroying (ω2) the multilayer composite structure (10) also includes a further step, the purpose of which is to achieve the flotation (S) of the sandwich structure (Z) on the surface (N1) of the first liquid medium (M1) after the bottom layer (101) is completely separated from the substrate (102). 13 ).

10. The method for preparing a (Ω) metal-containing film blank (1) according to claim 9, characterized in that: The stage of destroying (ω2) the multilayer composite structure (10) also comprises a further step aimed at achieving flotation (S) of the sandwich structure (Z) on the surface (N2) of the second liquid medium (M2) during chemical etching of the bottom layer (101). 14 ).

11. The method for preparing a (Ω) metal-containing film blank (1) according to claim 10, characterized in that: The stage of destroying (ω2) the multilayer composite structure (10) also comprises a further step aimed at achieving flotation (S) of the metal film (100) on the surface (N3) of distilled water (W) during the removal of the chemical reaction products. 15 ).

12. The method for preparing a (Ω) metal-containing film blank (1) according to claim 1, characterized in that: The substrate (102) comprises one of the following materials: (a) a single crystal silicon wafer; (b) a single crystal silicon wafer on which a graphene layer is pre-applied; (c) a single crystal silicon wafer containing silicon oxide; (d) a single crystal silicon wafer containing silicon oxide on which a graphene layer is pre-applied; (e) glass; (f) sapphire; (g) copper foil; (h) poly(4,4'-oxydiphenylene-tetramethylimide); (i) polyethylene terephthalate; (j) polyether; (k) polypropylene; (l) polyethylene; (m) polyvinyl chloride; (n) polystyrene; (o) polytetrafluoroethylene; (p) polymethyl methacrylate.

13. The method for preparing a (Ω) metal-containing film blank (1) according to claim 1, characterized in that: The first thickness (α) of the bottom layer (101) is comprised in a first range of 20 nm to 10000 nm, and The second thickness (β) of the metal film (100) is within a second range of 0.5 nm to 30 nm.

14. The method for preparing a (Ω) metal-containing film blank (1) according to claim 2, characterized in that: While the bottom layer (101) is separated from the substrate (102), the multilayer composite structure (10) is immersed (S8) in the first liquid medium (M1) along a guide line that forms an angle (μ) in a third range of 5° to 15° relative to the gravity vector (G).

15. The method for preparing a (Ω) metal-containing film blank (1) according to claim 1, characterized in that: The stage of forming (ω1) the multilayer composite structure (10) also comprises a further step aimed at coating (E3) the metal film (100) with a polymer protective layer (103).

16. The method for preparing a (Ω) metal-containing film blank (1) according to claim 15, characterized in that: The polymer comprises one of the following materials: (a) polymethyl methacrylate; (b) polydimethylsiloxane, (c) polycarbonate, (d) polylactic acid; (e) polyphthalamide; (f) bisphenol A.

17. A method for coating (Ψ) a target carrier (2) with a metal-containing film blank (1) produced by the production method (Ω) according to claim 1, wherein the coating (Ψ) method comprises a further step, the purpose of which is: · Transferring (Φ1) the metal-containing film blank (1) to the target carrier (2), Once the metal-containing membrane blank (1) has been transferred (Φ1) to the target carrier (2), the membrane blank (1) is dehumidified (Φ2).

18. A method for coating (Ψ) a target carrier (2) with a metal-containing film blank (1) prepared by the preparation method (Ω) according to claim 15, wherein the coating method (Ψ) comprises a further step, the purpose of which is: · Transferring (Φ1) the metal-containing film blank (1) to the target carrier (2), ·Remove (Φ 10 ) a polymer protective layer (103), Once the metal-containing membrane blank (1) has been transferred (Φ1) to the target carrier (2), the membrane blank (1) is dehumidified (Φ2).

19. Use of a target carrier (2) coated with a metal-containing film blank (1) according to the coating method (Ψ) of claim 17, which is used as one of the following products: (a) a transparent electrode; (b) a thin film solar cell; (c) a photodetector; (d) a light emitting diode; (e) a contact lens for the eye; (f) a flat screen; (g) a flexible screen; (h) a touch screen; (i) an electrochromic device; (j) a gas sensor; (k) a chemical sensor; (l) a biosensor; (m) a thin film type flexible nanoelectronic device.

20. Use of a target carrier (2) coated with a metal-containing film blank (1) according to the coating method (Ψ) of claim 18, which is used as one of the following products: (a) a transparent electrode; (b) a thin film solar cell; (c) a photodetector; (d) a light emitting diode; (e) a contact lens for the eye; (f) a flat screen; (g) a flexible screen; (h) a touch screen; (i) an electrochromic device; (j) a gas sensor; (k) a chemical sensor; (l) a biosensor; (m) a thin film type flexible nanoelectronic device.

Images