KR101182155B1 - Semiconductor device and method for forming metal thin film - Google Patents

Abstract

PURPOSE: A semiconductor device and a method of forming a metal thin film are provided to perform electroplating without the formation of a seed layer by adsorbing a metal nano particle on a high resistive substrate. CONSTITUTION: A diffusion barrier layer(106) is formed on a substrate. A natural oxide film exists on the surface of the diffusion barrier layer. A metal nano particle(108) is adsorbed on the surface of the diffusion barrier layer. A diameter of the metal nano particle is 1 to 6nm. A plating layer(110) covers the metal nano particle. The plating layer comprises one or more things among copper, silver, platinum, cobalt, and tin. An insulating layer is comprised of a first insulating layer(102) and a second insulating layer(104).

Description

Semiconductor device and method for forming metal thin film

The present invention relates to a semiconductor device and a method for forming a metal thin film, and more particularly, to a method for forming a metal thin film through electroplating after adsorbing metal nanoparticles and a semiconductor device manufactured using the same.

As semiconductor devices have been highly integrated, the speed of semiconductor devices has been greatly influenced by the RC speed delay between wirings, not the speed delay of gates. In order to solve this problem, low-resistance copper interconnects and low-dielectric dielectrics have been introduced. Currently, copper wiring is carried out using a method called a damascene process. The method of forming copper wiring using the damascene process includes chemical vapor deposition, physical vapor deposition, atomic layer deposition, and electrolytic / electroless plating electrodeposition. electroless deposition). Among them, electroplating is widely used because of the advantages of easy process conditions, low production costs, and the ability to form smooth thin film surfaces.

However, the electroplating method has a disadvantage in that a seed layer is required to transfer electricity when applied to a high resistivity substrate. Most seed layers use low-resistance copper and are formed on the diffusion barrier by physical vapor deposition. However, the conventional physical vapor deposition method, which has a weak step coverage due to the continuous reduction in semiconductor line width, has difficulty in forming a thinner and more uniform seed layer. Uneven seed layers can cause various defects after copper electroplating.

In order to solve this problem, direct electroplating, which directly forms a copper wire on the diffusion barrier layer without a seed layer, is currently considered as an alternative. In order to enable direct electroplating, studies are being actively conducted to replace the existing high-resistance tantalum (Ta) or titanium (Ti) -based diffusion barriers with ruthenium (Ru) and cobalt (Co), which are relatively easy to electrolytic plating. Although progress is being made, studies on ruthenium and cobalt diffusion barriers are still insufficient, and their performance is not as good as that of the existing seed layer.

An object of the present invention is to provide a method for forming a metal thin film capable of direct electroplating without a seed layer forming process, a micropattern of 35 nm or less, and an elemental electrodeposition, and a semiconductor device manufactured using the same.

One aspect of the invention relates to a semiconductor device. The semiconductor device includes a diffusion barrier layer on the substrate; Metal nanoparticles adsorbed on the diffusion barrier layer; And a plating film covering the metal nanoparticles.

The diffusion barrier layer may be titanium (Ti), tannium (Ta), tungsten (W), molybdenum (Mo), ruthenium (Ru), cobalt (Co) or nitride thereof.

The metal nanoparticles include any one or more of palladium (Pd), gold (Au), platinum (Pt), silver (Ag), copper (Cu), rhodium (Rh), nickel (Ni), and cobalt (Co). can do.

The particle diameter of the metal nanoparticles may be 1nm to 6nm.

The plating layer may include at least one of copper (Cu), silver (Ag), platinum (Pt), cobalt (Co), and tin (Sn).

Another aspect of the invention relates to a metal thin film forming method. The metal thin film forming method includes adsorbing metal nanoparticles on a substrate; And forming an electroplating film on the surface of the substrate through electroplating using the metal nanoparticles as a catalyst.

The substrate may include a diffusion barrier formed on the substrate, and before the adsorbing metal nanoparticles on the substrate, the substrate may include removing a natural oxide film present on a surface of the diffusion barrier.

The diffusion barrier layer may be titanium (Ti), tannium (Ta), tungsten (W), molybdenum (Mo), ruthenium (Ru), cobalt (Co) or nitride thereof.

The diffusion barrier layer may have a specific resistance of 10 μΩcm to 200 μΩcm.

In the step of removing the natural oxide film existing on the surface of the diffusion barrier, the natural oxide film may be removed by wet etching using an acidic solution.

Adsorbing the metal nanoparticles on the substrate may include forming the metal nanoparticles in a solution including a metal salt, a surfactant, and a reducing agent; Filtering the metal nanoparticles and redispersing the same in a solvent to prepare a surface activation solution; And contacting the surface activation solution with the substrate surface.

In the step of forming the metal nanoparticles with a solution containing the metal salt, a surfactant and a reducing agent, the metal salt is palladium (Pd), gold (Au), platinum (Pt), silver (Ag), copper (Cu), rhodium (Rh), nickel (Ni), ruthenium (Ru), or cobalt (Co) may include any one or more.

In the step of forming the metal nanoparticles with a solution containing the metal salt, surfactant and reducing agent, the surfactant is any one of PVP, CTAB, DTAB, MTAB, OTAB, TOPO, SDS, OAm, fatty amine, fatty acid or chlorine It may contain the above.

In the step of forming the metal nanoparticles with a solution containing the metal salt, a surfactant and a reducing agent, the reducing agent is ethylene glycol, TEG, ethanol, sodium borohydride, hydrazine, EDOT, D-glucose, CNCH ₂ COOK, glycerol, asco It may include any one or more of the big acid or sodium citrate.

In the step of forming an electroplating film on the surface of the substrate through the electroplating using the metal nanoparticles as a catalyst, the electroplating film is copper (Cu), silver (Ag), platinum (Pt), cobalt (Co) and tin ( Sn) may be included.

In the step of forming an electroplating film on the surface of the substrate through the electroplating using the metal nanoparticles as a catalyst, the pH of the plating solution for the electroplating is 1 to 13, the temperature of the plating solution may be 10 ℃ to 80 ℃ have.

In the step of forming an electroplating film on the surface of the substrate through the electroplating using the metal nanoparticles as a catalyst, the electroplating is performed by applying a constant voltage or a constant current or a pulse, the electrodeposition voltage is -0.2V to -1.5V Can be.

According to the present invention, by adsorbing metal nanoparticles on a high resistivity substrate, there is an advantage in that electroplating can be performed without forming a seed layer. In particular, in the semiconductor process, it is possible to form a metal thin film by electroplating directly without a seed layer on the diffusion barrier, it is possible to manufacture a fine pattern, and solve the problem of seed layer defects due to poor step coating property.

1 is a partial cross-sectional view of a semiconductor device in accordance with an embodiment of the present invention.
2 is a process flowchart of a metal thin film forming method according to an embodiment of the present invention.
Figure 3 is a graph measuring the surface charge of palladium nanoparticles synthesized according to an embodiment of the present invention according to pH.
FIG. 4 illustrates a linear sweep voltammetry (LSV) graph of a substrate that has undergone surface activation and a substrate that is not activated in a copper electroplating solution according to an embodiment of the present invention.
5 is an electron micrograph of the surface after constant voltage electrodeposition for 50 seconds at -750 mV compared to a standard caramel electrode.

Hereinafter, an embodiment of a semiconductor device and a metal thin film forming method according to the present invention will be described with reference to the accompanying drawings. In this process, the thickness of the lines or the size of the components shown in the drawings may be exaggerated for clarity and convenience of description. Further, terms to be described below are defined in consideration of the functions of the present invention, which may vary according to the intention or custom of the user, the operator. Therefore, the definitions of these terms should be made based on the contents throughout the specification.

1 is a partial cross-sectional view of a semiconductor device in accordance with an embodiment of the present invention. Referring to FIG. 1, a semiconductor device according to an embodiment of the present invention may include a substrate 100, insulating films 102 and 104, a diffusion barrier film 106, metal nanoparticles 108, an electroplating film 110, and a cap. Ping film 112 and the like. The illustrated example shows a metal wiring constituting an integrated circuit semiconductor device, but the invention is not limited to the wiring structure shown.

The insulating layers 102 and 104 may be a multilayer thin film formed of the first insulating layer 102 and the second insulating layer 104. As another example, the insulating film may be one insulating film that does not distinguish between the first insulating film 102 and the second insulating film 104. In some cases, such an insulating film may not exist. The insulating layers 102 and 104 may include an organic insulator or an inorganic insulator. For example, it may be an insulator including silicon oxide (SiO ₂ ). For example, black diamond, fluorine silicate glass (FSG), SiOC, polyimide, hydrogen silsesquioxanes (HSQ), poly alylene ethers (PAE), bisbenzocycle butenes (BCB), fluoro-polyimides (FPI), fluoro (EPI) -polyinide), amorphous fluorocarbon (α-C: F, amprphous flurorocarbon), parylene, PTEEE (polyfluro tetraethylene), nanoporous silica and the like, but the present invention is not limited to the above-described type of insulator.

The diffusion barrier layer 106 may be a high resistivity metal layer or a metal nitride layer. The diffusion barrier layer 106 may serve to prevent the metal atoms constituting the electroplating layer 110 from diffusing into the insulating layers 102 and 104. For example, titanium (Ti), tantalum (Ta), tungsten (W), molybdenum (Mo), ruthenium (Ru), cobalt (Co) or nitrides thereof, and the like, and chemical vapor deposition (CVD) : It may be formed by a physical vapor deposition (PVD) method such as chemical vapor deposition (PSPD) or sputtering, but the material and formation method of the diffusion barrier layer 106 are not limited.

The metal nanoparticles 108 are metal nanoparticles that are adsorbed on the surface of the diffusion barrier layer 106 and may function as nuclei of the initial electroplating. The metal nanoparticles 108 may be any one or more of palladium (Pd), gold (Au), platinum (Pt), silver (Ag), copper (Cu), rhodium (Rh), nickel (Ni), and cobalt (Co). It may be a nanoparticle comprising a. It is preferable that the particle diameter of the metal nanoparticle 108 is 6 nm or less. In the case of 6 nm or less, the increase in resistance of the thin film due to the metal nanoparticles may be reduced, and it may be easily applied to the recent micropattern process of 35 nm or less. In consideration of the manufacturing advantages, the particle size of the metal nanoparticles may be more effective to be 1nm to 6nm.

The electroplating film 110 is formed by electroplating with the metal nanoparticles 108 as a catalyst, and any of copper (Cu), silver (Ag), platinum (Pt), cobalt (Co), and tin (Sn). It may include one or more. The capping film 112 may be present on the electroplating film 110. The camping film 112 may be made of various materials such as silicon nitride, silicon carbide, CoWP, cobalt nitride, Ta-containing capping film, and the capping film 112 may not be limited in material and formation method.

2 is a process flowchart of a metal thin film forming method according to an embodiment of the present invention. Referring to FIG. 2, first, a natural oxide film existing on a substrate may be removed (S100). When it is mentioned in the present invention that a film (layer) is on another film (layer) or substrate 'top', 'top' it is formed directly on another film (layer) or substrate as well as other films between them ( Layer) is included.

On the other hand, the natural oxide film removal process may be omitted in some cases. That is, the process may be omitted in the case where the process proceeds to the in-line process or the natural oxide film is insignificant.

A natural oxide film may be present on the surface of the metal film or the metal nitride film of the substrate on which the diffusion barrier film (high resistivity metal film or metal nitride film) is formed (hereinafter used in combination with the 'high resistivity substrate'), and to help uniformly adsorb the metal nanoparticles. It is preferable to remove the natural oxide film present on the surface of the high resistivity metal film or the metal nitride film. The high resistivity metal film or metal nitride film is a diffusion preventing function, for example, titanium (Ti), tantalum (Ta), tungsten (W), molybdenum (Mo), ruthenium (Ru), cobalt (Co) ) Or nitrides thereof. In addition, the specific resistance may range from 10 μΩcm to 200 μΩcm.

There is no limit to the removal method of the natural oxide film. For example, it may be removed by wet etching using an acidic etching solution. For another example, it may be removed by dry etching using plasma gas.

As an example of an acidic solution for removing a natural oxide layer, a mixed solution of hydrofluoric acid (HF) and nitric acid (HNO ₃ ) may be mentioned. The concentration of the etching solution may be 1 vol% to 10 vol% hydrofluoric acid, 1 vol% to 10 vol% nitric acid, preferably 1 vol% to 5 vol% hydrofluoric acid, and 1 vol% to 5 vol% nitric acid. . The time to be treated with the etching solution may vary depending on the type and thickness of the high resistivity metal film or the metal nitride film, but may be 3 to 30 minutes.

Next, metal nanoparticles are adsorbed on the surface of the high resistivity metal film or the metal nitride film from which the natural oxide film is removed (S200). Adsorption of the metal nanoparticles may use a method of immersing a solution containing the metal nanoparticles into a substrate or dropping the solution onto the substrate. As another example, the metal nanoparticles may be directly formed on the diffusion barrier by vapor phase synthesis.

Hereinafter, metal nanoparticles are formed (S2001), the metal nanoparticles are redispersed in a solvent to prepare a surface activation solution (S2002), and the surface activation solution is brought into contact with the substrate (S2003) to adsorb the metal nanoparticles. Explain based on how to make it.

Looking at the manufacturing method of the metal nanoparticles, both of the metal nanoparticles are produced by the dry method or by the wet method can be utilized in the present invention. That is, the metal nanoparticle manufacturing process is not particularly limited unless it is a problem to make a surface activation solution. For example, nanoparticles such as copper (Cu), nickel (Ni), and cobalt (Co) may be manufactured by an arc discharge method, a stuttering method, or cryomelting. For example, it is composed of platinum (Pt), palladium (Pd), gold (Au), nickel (Ni), silver (Ag) and the like by a liquid phase method (wet method) such as pyrolysis and precipitation of an organometallic compound. Nanoparticles can be prepared.

The metal nanoparticles include any one or more of palladium (Pd), gold (Au), platinum (Pt), silver (Ag), copper (Cu), rhodium (Rh), nickel (Ni), and cobalt (Co). It may be a nanoparticle. The size of the nanoparticles will vary depending on the thickness of the thin film to be electrodeposited, but may be preferably 6 nm or less, more preferably 1 nm to 6 nm.

Looking at one example of the production of metal nanoparticles by the wet method, metal nanoparticles can be prepared from a solution containing a metal salt, a surfactant and a reducing agent. The metal salt may be a metal salt including palladium (Pd), gold (Au), platinum (Pt), silver (Ag), copper (Cu), rhodium (Rh), nickel (Ni) or cobalt (Co), The concentration of the metal salt may be 0.001M to 0.02M.

There is no limitation to the surfactant. For example, polyvinylpyrrolidone (PVP), cetyltrimethylammonium Bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), meristyltrimethylammonium bromide (MTAB), octadecyltrimethylammonium bromide (OTAB), tri-n-octylphosphineoxide (DOO), and ODSAsm (sulfate) oleylamine, fatty amine, fatty acid, or chlorine.

The concentration of the surfactant is preferably 0.010M to 0.200M for PVP and 0.001M to 0.020M for CTAB.

There are no restrictions on the reducing agent: ethylene glycol, TEG (tetraethylene glycol), ethanol, sodium borohydride, hydrazine, EDOT (3,4-ethylenedioxythiophene), D-glucose, CNCH ₂ COOK, glycerol, ascorbic acid (Ascorbic acid) or sodium citrate can be used a reducing agent containing at least one.

Thereafter, the precipitated metal nanoparticles may be separated (filtered) and washed, followed by solvent (re) dispersion to prepare a surface activation solution. The solvent for dispersing (redispersing) the metal nanoparticles after filtering is not limited, but water or alcohol may be used. Preferably, alcohols such as ethanol and butanol having excellent dispersibility can be used.

Thereafter, the prepared surface activation solution may be contacted with the substrate to adsorb the metal nanoparticles onto the substrate. The density of the nanoparticles adsorbed on the high resistivity substrate will depend on the concentration of the surface activation solution containing the nanoparticles and the volume of the solution applied per unit area, but preferably between 0.1 g / L and 0.4 g / L When using the surface activation solution of the volume of the surface activation solution applied to 1.5cm X 1.5cm is preferably 0.05mL to 0.2mL.

In addition, since the nanoparticles of the surface activation solution will be adsorbed onto the substrate by the surface charge difference after being applied to the high resistivity substrate, it is possible to dry the high resistivity substrate activated by the metal nanoparticles, but there is no effect on subsequent electroplating without drying. In addition, when the high resistivity substrate is treated with the surface activation solution, the temperature of the surface activation solution is preferably 10 ° C to 90 ° C. When the high resistivity substrate is dried, natural drying and vacuum drying are possible, and a method of subliming the solution at subzero temperatures is also possible.

Next, a metal thin film (electrolytic plating film) is formed on the surface of the substrate through electroplating (S300). The electroplating film may be formed in a single layer or multiple layers. When forming a multilayer, different metals may be electroplated, or the same metal may be electroplated in multiple layers.

Electroplating may be performed by placing a substrate surface-activated with nanoparticles in an electroplating solution (plating solution) in an air atmosphere and a temperature condition of 10 ° C to 80 ° C and then applying a reduction potential. There is no restriction on the plating solution for electroplating. For example, copper (Cu), silver (Ag), platinum (Pt), cobalt (Co), tin (Sn) plating liquid, etc. are mentioned. The concentration of metal ions in the plating liquid is preferably 0.1M to 0.5M.

In electroplating, it is performed by applying constant voltage or constant current or applying pulse. The applied reduction potential (electrode voltage) may be -0.2V to -1.5V with respect to the standard calomel electrode, but depending on the characteristics of the plating solution. Can vary. In addition, during electroplating, a constant voltage, a constant current, or a pulse may be applied. The electrodeposition current may be 0.1 mA to 50 mA, and the pH range of the plating liquid may be 1 to 13, preferably 1 to 10.

When the plating solution is a copper electroplating solution, the preferred copper ion concentration of the copper electroplating solution is 0.1M to 0.5M, and the preferred reduction potential is -0.2V to -1.5V. The pH of the copper electroplating solution is suitably between 1 and 9. In addition, in the case of other electroplating solutions, the concentration of metal ions is preferably 0.1M to 0.5M.

In addition, the electrodeposition time for forming the metal thin film from the plating liquid may vary depending on the applied voltage and the target thickness, but may preferably be 3 seconds to 10,000 seconds.

An example of forming a metal thin film on a high resistivity substrate according to the present invention is as follows.

In order to remove the oxide film formed on the surface of a high resistivity substrate such as tantalum, the surface of the tantalum is etched with an etching solution containing 1 vol% to 5 vol% hydrofluoric acid and 1 vol% to 5 vol% nitric acid for 3 to 10 minutes. Nanoparticle solution containing 1 nm to 6 nm palladium, gold, platinum, silver, copper, rhodium, nickel, ruthenium, or cobalt nanoparticles synthesized by wet or dry methods on the etched surface at a concentration of 0.005M to 0.010M Surface activation solution) to a high resistivity substrate at a volume of 0.05 ml to 0.1 ml per 1.5 cm X 1.5 cm. At this time, the temperature of the surface activation solution is 10 ℃ to 90 ℃ and the temperature of the high resistivity substrate is also maintained at 10 ℃ to 90 ℃, the pH of the surface activation solution is maintained between 3 to 10. Surface treatment may or may not dry the nanoparticle solution completely or completely. The surface-activated substrates with nanoparticles were used with copper electroplating solutions of 0.1M to 0.5M or other metal electroplating solutions of 0.1M to 0.5M for the standard calomel electrode for copper at temperatures between 10 ° C and 80 ° C. Electrodeposit is performed at -0.2V to -1.5V for 3 to 400 seconds depending on the reduction potential.

The metal thin film formed by the above method may have a thickness of 30 nm to 200 nm and a surface roughness of 5 nm to 15 nm by surface analysis.

< Example >

Copper Electroplating on Tantalum Substrates Surface-activated with Palladium Nanoparticles

1. Preparation of Palladium Nanoparticle Solution

Palladium nanoparticles were synthesized using a polyol method using ethylene glycol. First, 0.1 M of polyvinylpyrrolidone (PVP) and 0.01 M CTAB (cetyltrimethylammonium Bromide) are added to ethylene glycol as a solvent. Thereafter, 0.01 M of K ₂ PdCl ₆ was added.

The palladium solution prepared as above was reduced for 80 seconds using microwave. The synthesized palladium nanoparticle solution was extracted by using a centrifuge (5000 rpm, 15 minutes), and then washed with ethanol and hexane (hexane) sequentially (ethanol: hexane = 1: 4), and finally, the palladium nanoparticles were washed. Centrifuge again (5000 rpm, 15 minutes) and extracted and stored in ethanol dispersed.

2. Surface activation and copper electroplating using palladium nanoparticles

The substrate used in the experiment was a flat wafer on which a tantalum diffusion barrier was formed by physical vapor deposition, which had a structure of Ta (15 nm) / TaN (15 nm) / SiO ₂ and cut into a square shape of 1.5 cm x 1.5 cm. Was used.

In order to remove the oxide film formed on the surface of the tantalum substrate prepared as described above, it was immersed in an etching solution mixed with 1 vol% hydrofluoric acid and 1 vol% nitric acid for 5 minutes, and the surface was washed three times with ion removal water for 10 seconds. Thereafter, 0.1 ml of the palladium nanoparticle solution dispersed in the ethanol was slowly dropped on the surface of the substrate, and then dried at room temperature for about 1 hour.

The substrate subjected to the surface activation was immersed in a copper electroplating solution consisting of 0.25M Cu ₂ P ₂ O ₇ and 1M K ₄ P ₂ O ₇ to perform electroplating. A standard calomel electrode was used as the reference positive electrode, and a platinum wire was used as the counter electrode.

Figure 3 is a graph measuring the surface charge of palladium nanoparticles synthesized according to an embodiment of the present invention according to pH. Referring to FIG. 3, the surface charge of the formed palladium nanoparticles was measured for each pH using a zeta potential analyzer, and the pH was adjusted using 0.1 M potassium hydroxide and 0.1 M sulfuric acid. It can be seen that the surface charge of the palladium nanoparticles had a negative value regardless of the pH within the pH range of 2 and 12, and the absolute value increased with increasing pH.

FIG. 4 illustrates a linear sweep voltammetry (LSV) graph of a substrate that has undergone surface activation and a substrate that is not activated in a copper electroplating solution according to an embodiment of the present invention. Through surface activation, when the palladium nanoparticles are present on the surface of the substrate, the onset potential is present at the higher side and the reduction current is also large. This is because the palladium nanoparticles present on the diffusion barrier layer smoothly induce initial nucleation by reducing charge transfer resistance among various resistances generated during electroplating.

5 is an electron micrograph of the surface after constant voltage electrodeposition for 50 seconds at -750 mV compared to a standard caramel electrode. The substrate that did not undergo surface activation did not form a thin film due to uneven copper nucleation, but the substrate that proceeded with surface activation induced smooth nucleation by palladium nanoparticles to confirm that a continuous copper thin film was formed. Could.

The present invention is to proceed with electroplating after removing the natural oxide film on the diffusion barrier and adsorbing nanoparticles instead of forming a seed layer on the diffusion barrier to form a growth nucleus necessary for the reduction of metal ions during electroplating. The metal nanoparticles adsorbed on the diffusion barrier layer can smoothly induce the initial nucleation by reducing the charge transfer resistance among various resistances generated during electrolytic plating. Therefore, a uniform and smooth thin film can be formed. On the other hand, when electroplating is performed on the diffusion barrier layer without surface activation, the charge transfer resistance is so large that the growth of the initial metal is not performed smoothly, resulting in a non-uniform and rough film. In addition, by adsorbing the metal nanoparticles to reduce the increase of resistance by the metal nanoparticles as much as possible, it is possible to easily produce a fine pattern of 35nm or less, there is an advantage that can be an elemental electrodeposition.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. will be. In addition, the illustrated semiconductor device is merely exemplary, and the technical spirit of the present invention may be applied to other semiconductor devices. Accordingly, the true scope of the present invention should be determined by the following claims.

100 substrate 102 first insulating film
104: second insulating film 106: diffusion barrier
108: metal nanoparticles 110: electroplating film
112: capping film

Claims (17)

A diffusion barrier film present on the substrate;
Metal nanoparticles adsorbed on the diffusion barrier layer; And
A plating film covering the metal nanoparticles;
&Lt; / RTI &gt;
The method of claim 1,
The diffusion barrier layer is titanium (Ti), tantalum (Ta), tungsten (W), molybdenum (Mo), ruthenium (Ru), cobalt (Co) or a nitride thereof.
The method of claim 1,
The metal nanoparticles include any one or more of palladium (Pd), gold (Au), platinum (Pt), silver (Ag), copper (Cu), rhodium (Rh), nickel (Ni), and cobalt (Co). Semiconductor device.
The method of claim 1,
A particle size of the metal nanoparticles is 1nm to 6nm.
The method of claim 1,
The plating film includes at least one of copper (Cu), silver (Ag), platinum (Pt), cobalt (Co), and tin (Sn).
Adsorbing metal nanoparticles on the substrate; And
Forming an electroplating film on the surface of the substrate through electroplating using the metal nanoparticles as a catalyst;
Metal thin film forming method comprising a.
The method of claim 6,
The substrate includes a diffusion barrier formed on the substrate, and before the step of adsorbing the metal nanoparticles on the substrate, removing the natural oxide film existing on the surface of the diffusion barrier film forming method.
The method of claim 7, wherein
The diffusion barrier layer is titanium (Ti), tantalum (Ta), tungsten (W), molybdenum (Mo), ruthenium (Ru), cobalt (Co) or a nitride thereof.
The method of claim 7, wherein
The diffusion barrier has a specific resistance of 10μΩcm to 200μΩcm Metal thin film formation method.
The method of claim 7, wherein
Removing the natural oxide film present on the surface of the diffusion barrier layer, wherein the natural oxide film is removed by wet etching using an acidic solution.
The method of claim 6,
Adsorbing the metal nanoparticles on the substrate
Forming metal nanoparticles with a solution comprising a metal salt, a surfactant, and a reducing agent;
Filtering the metal nanoparticles and redispersing the same in a solvent to prepare a surface activation solution; And
Contacting the surface activation solution with the substrate surface;
Metal thin film forming method comprising a.
The method of claim 11,
In the step of forming the metal nanoparticles with a solution containing the metal salt, a surfactant and a reducing agent, the metal salt is palladium (Pd), gold (Au), platinum (Pt), silver (Ag), copper (Cu), rhodium (Rh), nickel (Ni), ruthenium (Ru), or a metal salt comprising a metal salt containing at least one of cobalt (Co).
The method of claim 11,
In the step of forming the metal nanoparticles with a solution containing the metal salt, surfactant and reducing agent, the surfactant is any one of PVP, CTAB, DTAB, MTAB, OTAB, TOPO, SDS, OAm, fatty amine, fatty acid or chlorine Metal thin film forming method comprising the above.
The method of claim 11,
In the step of forming the metal nanoparticles with a solution containing the metal salt, surfactant and reducing agent, the reducing agent is ethylene glycol, TEG, ethanol, sodium borohydride, hydrazine, EDOT (3,4-ethylenedioxythiophene), D-glucose, CNCH ₂ COOK, glycerol, ascorbic acid or sodium citrate any one or more metal thin film forming method.
The method of claim 6,
In the step of forming an electroplating film on the surface of the substrate through the electroplating using the metal nanoparticles as a catalyst, the electroplating film is copper (Cu), silver (Ag), platinum (Pt), cobalt (Co) and tin ( Method for forming a metal thin film comprising at least one of Sn).
The method of claim 6,
In the step of forming an electroplating film on the surface of the substrate through the electroplating using the metal nanoparticles as a catalyst, the pH of the plating solution for the electroplating is 1 to 13, the temperature of the plating solution is 10 ℃ to 80 ℃ Thin film formation method.
The method of claim 6,
In the step of forming an electroplating film on the surface of the substrate through the electroplating using the metal nanoparticles as a catalyst, the electroplating is performed by applying a constant voltage or a constant current or a pulse, the electrodeposition voltage is -0.2V to -1.5V Phosphorus metal thin film formation method.

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