KR20130070962A - Electronic device and methods of manufacturing for the same with graphene layer for metal diffusion barrier - Google Patents

Abstract

PURPOSE: An electric component having a metal diffusion prevention graphene layer and a manufacturing method there of form a graphene layer between a bonding layer and a metal layer, increasing reproducibility. CONSTITUTION: A metal layer (203) comprises single metal or alloy. A graphene layer (202) is formed on the lower side of the metal. The thickness of the graphene layer is 0.2nm to 1.5μm. A bonding layer (201) is formed one the lower side of the graphene. The bonding layer is formed with one or more of single metal film, alloy film, oxide film, organic layer or inorganic film.

Description

Electronic device and method of manufacturing for the same with Graphene Layer for Metal Diffusion Barrier}

The present invention relates to an electronic device and a manufacturing method, and more particularly, to form a metal diffusion prevention graphene layer between the bonding layer and the metal layer included in a light emitting diode (LED) or a semiconductor device, The present invention relates to an electronic device and a manufacturing method provided with a graphene layer for preventing metal diffusion that prevents metal ions of a metal layer from diffusing to a bonding layer or diffusion of ions from a bonding layer into a metal layer by heat.

Semiconductor devices or light emitting diodes are key devices in the electromechanical field. The semiconductor device or the light emitting diode includes a bonding layer and a metal layer. When the bonding layer is brought into contact with the metal layer, a heat treatment or a pressing process is performed, whereby metal ions included in the metal layer are diffused into the bonding layer by heat or pressure, or the bonding layer is formed. Metal ions in the layer diffuse into the metal layer.

Therefore, various techniques have been introduced to improve the problem that the metal ions of the metal layer or the metal ions of the bonding layer are diffused by heat or pressure by forming the metal diffusion preventing layer between the bonding layer and the metal layer.

1A is a cross-sectional view of a light emitting diode device having a diffusion barrier according to the prior art. As shown, the light emitting diode device 100 has a bonding layer 103, a diffusion barrier film 104, a first ohmic bonding metal layer 105, a light emitting diode unit 106, and a second ohmic bonding on an upper surface of the substrate 102. The metal layer 107 is formed.

The diffusion barrier film 104 is made of a metal, and the metal is titanium (Ti), nickel (Ni), ruthenium (Ru), tantalum (Ta), tungsten (W), zirconium (Zr) or molybdenum (Mo). It includes any one of.

However, since the cost of the metal constituting the diffusion barrier film 104 is high, the manufacturing cost of the semiconductor device or the light emitting diode is increased.

1B to 1C are cross-sectional views of a semiconductor device having a diffusion barrier according to the prior art. As shown in FIG. 1B, the gate insulating layer 108, the polysilicon layer 109, the titanium film 110, the tungsten nitride film 111, and the tungsten layer 112 are included on the substrate 102. 1C illustrates a gate insulating film 108, a polysilicon layer 109, a titanium layer 113, a titanium nitride layer 114, an amorphous film 115, and a tungsten layer 112 formed on the substrate 102. do.

1B includes a double structure of the titanium film 110 and the tungsten nitride film 111 to prevent the tungsten ions of the tungsten layer 112 from diffusing into the polysilicon layer 109, and FIG. In order to prevent the tungsten ions of the layer 112 from diffusing into the polysilicon layer 109, the titanium layer 113 is formed and then the titanium layer 113 and the titanium nitride layer 114 are formed through a nitriding process.

Further, the titanium layer 113 and the titanium nitride layer 114 of FIG. 1C are formed of a material of either tantalum-tantalum nitride or titanium silicon-titanium nitride silicon.

However, when the diffusion barrier is formed in a double structure in Figure 1b, there is a problem that the thickness of the diffusion barrier is increased to increase the process difficulty of the subsequent gate etching process, when the diffusion barrier is formed of nitride in Fig. Nitride heat treatment process after deposition, there is a problem of low reproducibility.

Accordingly, the present invention is to solve the above-described problems, to reduce the thickness of the metal diffusion prevention graphene layer, to reduce the manufacturing cost of the electronic device, in the manufacturing of the electronic device, to prevent the metal diffusion to increase reproducibility It is an object of the present invention to provide an electronic device and a manufacturing method provided with a graphene layer.

In order to achieve the above object, an electronic device having a graphene layer for preventing metal diffusion according to the present invention may be formed on a metal layer made of a single metal or an alloy, a graphene layer formed on a bottom surface of a metal layer, or a bottom surface of a graphene layer. It characterized in that it comprises a bonding layer (bonding layer).

Furthermore, when m bonding layers and m metal layers are repeatedly formed on the metal layer, m-1 layers of graphene are formed between the bonding layer and the metal layer, and m bonding layers are formed on the metal layer. And when m metal layers are repeatedly formed, m graphene layers are formed between the bonding layer and the metal layer.

As described above, the present invention forms a graphene layer for preventing metal diffusion between the bonding layer and the metal layer, so that the metal ions contained in the metal layer are diffused into the bonding layer, or the metal ions contained in the bonding layer are diffused into the metal layer. prevent.

Furthermore, forming the graphene layer having the thinnest layer of graphite between the bonding layer and the metal layer reduces the thickness and process difficulty of the metal diffusion barrier layer, reduces the manufacturing cost of the electronic device, and increases the reproducibility. .

1A to 1B are cross-sectional views of a light emitting diode device or a semiconductor device with a diffusion barrier according to the prior art.
2 is a view illustrating an electronic device having a graphene layer for preventing metal diffusion according to an embodiment of the present invention.
3 is a photograph illustrating a structure after heat treatment of an electronic device that does not include a conventional graphene layer and an electronic device including the graphene layer of the present invention.
4A to 4B illustrate an electronic device having a graphene layer for preventing metal diffusion according to another embodiment of the present invention.
5A to 5B are views illustrating a method for manufacturing an electronic device having a graphene layer for preventing metal diffusion according to an embodiment of the present invention.
6A to 6B are diagrams illustrating a light emitting diode device and a semiconductor device according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings. Prior to this, the terms or words used in this specification and claims should not be construed as being limited to the ordinary or dictionary meanings, and the inventors properly define the concept of terms in order to explain their invention in the best way. It should be interpreted as meanings and concepts in accordance with the technical idea of the present invention based on the principle that it can.

Therefore, the embodiments described in the specification and the drawings shown in the drawings are only the most preferred embodiment of the present invention and do not represent all of the technical idea of the present invention, various equivalents that may be substituted for them at the time of the present application It should be understood that there may be water and variations.

2 is a view illustrating an electronic device having a graphene layer for preventing metal diffusion according to an embodiment of the present invention. As shown in FIG. 2A, the electronic device 200 includes a metal layer 203 formed of a single metal or an alloy, a graphene layer 202 formed on the bottom surface of the metal layer 203, and a bottom surface of the graphene layer 202. A bonding layer 201 is formed on the.

Further, the metal layer 203 may be formed of lithium (Li), beryllium (Be), boron (B), sodium (Na), magnesium (Mg), aluminum (Al), silicon (Si), indium (In), and sulfur (S). ), Potassium (K), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni ), Copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), rubidium (Rb), strontium (Sr), yttrium (Y), zirconium ( Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), indium (In), tin (Sn), tellurium (Te), antimony (Sb), barium (Ba), Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Gadolinium (Gd), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Iridium (Ir), It is formed of a single metal made of at least one of lead (Pb), bismuth (Bi), polonium (Po), silver (Ag), platinum (Pt), gold (Au) or uranium (U), or is formed of an alloy. .

Furthermore, the alloy is composed of at least one of a binary alloy consisting of two kinds of components, a ternary alloy consisting of three kinds of components, or a multicomponent alloy, wherein a binary alloy, tertiary alloy, or a multicomponent alloy is formed of at least one material of the single metal. Combined or the single metal with helium (He), boron (B), carbon (C), nitrogen (N), oxygen (O), fluorine (F), neon (Ne), silicon (Si), phosphorus (P) ), Sulfur (S), chlorine (Cl), argon (Al), arsenic (As), selenium (Se), bromine (Br), krypton (Kr), tellurium (Te), iodine (I), xenon (Xe), astatin (At) or radon (Rn) any one or more of the base metal is bonded.

In addition, the graphene layer 202 is a layer of graphite in which hexagonal honeycomb-shaped layers of carbon are stacked one by one. Among two-dimensional planar structures or structures in which graphite and heteroatoms are bonded by doping heterogeneous atoms in graphite. It is composed of either structure.

Further, the graphene layer 202 is formed to a thickness of 0.2nm to 1.5㎛. When the thickness of the graphene layer 202 is thicker than 1.5 μm, the graphene disappears, the graphite appears, and light transmittance and resistance increase.

It has greater electrical conductivity, light transmittance than metal, and is characterized by flexibility.

In one embodiment, tungsten has an electrical conductivity of 1.87 × 10 ⁵ / cm · ohm and graphene has an electrical conductivity typical value of 8 × 10 ⁵ / cm · ohm, indicating that the graphene has a higher electrical conductivity. Can be. As the electrical conductivity of the graphene is high, the graphene facilitates charge transfer between the bonding layer and the metal layer to serve as a charge carrier, and increases the electrical characteristics of the electronic device 200.

Furthermore, graphene facilitates the fabrication of small electronic devices by increasing the electrical conductivity of graphene as defects are added.

In one embodiment, the Au Grid substrate transparent electrode is 74%, and the light transmittance of graphene is about 90% to 97%. Graphene has a lower light absorption loss than a metal, so it can be applied to a semiconductor or a light emitting diode that requires high light transmittance, and the graphene layer absorbs light at a high speed so that light transmission is good and resolution is increased.

In addition, the graphene is flexible, even if it is disposed in a non-flat state on the upper surface of the bonding layer, it is rearranged to be parallel to the bonding layer through heat treatment or pressing. Since the graphene is disposed in parallel with the bonding layer, the defect rate is reduced during the semiconductor or light emitting diode manufacturing process, and light or laser is uniformly irradiated. In addition, when forming the metal layer formed on the graphene layer upper surface, it is possible to form a metal layer having a uniform surface.

In one embodiment, the bonding layer 201 is formed of at least one of a single metal film, an alloy film, an oxide film, an organic film, or an inorganic film, and the single metal film and the alloy film constitute a single metal or alloy forming the metal layer 203. It may be made of the same material as.

Furthermore, the oxide film is a film made of an oxide that is a binary compound of oxygen and other elements. In one embodiment, the bonding layer 201 is a gold oxide (Au ₂ O) formed by combining single metal gold (Au) and oxygen. ₃ ) can be formed.

In addition, the organic film is a film made of an organic compound including all carbon compounds except for oxides of carbon or carbonates of metals. In one embodiment, ethyl hexanoate, acetylacetonate, and dialkyl. Dialkyldithiocarbamates, Carboxylic acids, Carboxylates, Pyridine, Diamines, Arsines, Diarsines, Phosphines Diphosphines, Butoxide, Isopropoxide, Ethoxide, Chloride, Acetate, Carbonyl, Carbonate, Carbonate, At least one of hydroxide, arenes, beta-diketonate, 2-nitrobenzaldehyde, or acetate dihydrate It is formed from organic material.

In addition, the inorganic film is a film made of all compounds except hydrocarbons and derivatives thereof, and inorganic materials including metal or nonmetallic simple materials, and includes a single metal film and an alloy film.

3 is a photograph illustrating a structure after heat treatment of an electronic device that does not include a conventional graphene layer and an electronic device including the graphene layer of the present invention. In one embodiment, the structure of the electronic device 200 used in the experiment is composed of a glass substrate (Glass Substrate), a silver (Ag) bonding layer and a gold tin alloy (AuSn) metal layer. Before the heat treatment, the thickness of the silver (Ag) bonding layer and the thickness of the tin alloy (AuSn) metal layer were 3000 kPa, respectively.

3 (a) shows a structure in which the electronic device 200 without the graphene layer 202 is heat-treated, the silver (Ag) bonding layer has a thickness of 1590 kPa, and the thickness of the tin alloy metal layer (AuSn) is 3420 kPa. to be. As shown, silver (Ag) ions in the silver (Ag) bonding layer diffuse into the tin alloy (AuSn) metal layer, so that the thickness of the silver (Ag) bonding layer is reduced than before the heat treatment, and the tin (AuSn) metal layer It can be seen that the thickness of is increased.

However, FIG. 3 (b) shows that the graphene layer 202 is included 5 nm (not shown) between the silver (Ag) bonding layer and the tin alloy (AuSn) metal layer, and thus the silver (Ag) bonding layer. Of silver (Ag) ions is prevented from diffusing into the tin-tin (AuSn) metal layer, and after heat treatment, the thickness of the silver (Ag) bonding layer and the thickness of the tin-tin (AuSn) metal layer are similar to the thickness before the heat treatment. Can be.

The thickness change of the silver (Ag) bonding layer and the tin-tin alloy (AuSn) metal layer shown in FIG. 3 (b) can be seen as an experimental error range depending on the measurement position before the heat treatment and the measurement position after the heat treatment.

4A to 4B illustrate an electronic device having a graphene layer for preventing metal diffusion according to another embodiment of the present invention. As shown, the electronic device 200 of FIG. 4A further includes a bonding layer 201, a graphene layer 202, and a metal layer 203 on an upper surface of the metal layer 203.

Furthermore, the electronic device 200 includes a plurality of bonding layers 201, graphene layers 202, and metal layers 203 formed on the upper surface of the metal layer 203, such that the bonding layer 201, the graphene layers 202, and the metal layers are formed. 203 may be formed in a stacked structure of 1 to m pieces.

In addition, the electronic device 200 of FIG. 4B further includes a bonding layer 201 and a metal layer 203 on the upper surface of the metal layer 203, and the bonding layer 201 and the metal layer 203 are formed on the upper surface of the metal layer 203. It may be formed of a stacked structure of pieces to m.

In addition, the electronic device 200 according to the present invention may have a structure in which the structure of FIG. 4A and the structure of FIG. 4B are combined. The bonding layer 201, the graphene layer 202, the metal layer 203, the bonding layer 201 and the metal layer 203 on the upper surface of the metal layer 203, the graphene layer 202 in the electronic device 200 At least one is formed.

In the graphene layer 202 of the electronic device 200 illustrated in FIGS. 4A to 4B, when one to m graphene layers 202 are generated, all m pieces have the same thickness or at least one of m pieces. The thickness of the at least one graphene layer 202 is different.

5A to 5B are views illustrating a method for manufacturing an electronic device having a graphene layer for preventing metal diffusion according to an embodiment of the present invention. As shown, the method of manufacturing the electronic device 200 includes forming a graphene layer 202 on the top surface of the bonding layer 201 (s101), and forming a metal layer 203 on the top surface of the graphene layer 202. (s102).

Further, the graphene layer 202 may be formed by thermal vapor deposition, chemical vapor deposition (CVD), physical vapor deposition (PVD), sputtering, and co-evaporation. ), Spin Coating, Doctor Blade, Spraying Coating, Screen Printing, Ink-Jet printing, Pad Printing, Gravure Printing It is formed by any one of Printing, Offset Lithography Printing, Roll to Roll (R2R) or Transfer method.

Further, the transfer method may be spin coating, soft transfer printing using polydimethylsiloxane (PDMS), transfer method using poly-methymethacrylate (PMMA), transfer method using heat release tape, or transfer method using roll. There is this.

6A to 6B are diagrams illustrating a light emitting diode device and a semiconductor device according to an embodiment of the present invention. As shown, FIG. 6A includes a substrate 204, a bonding layer 201, a graphene layer 202, a metal layer 203, a light emitting diode portion 205, and an ohmic contact metal layer 206.

Further, when manufacturing the light emitting diode device 500, the bonding layer 201 is composed of gold (Au) or a gold-containing alloy, the metal layer 203 is a p- ohmic contact metal, the ohmic contact metal is n- ohmic contact Made of metal. Components of the bonding layer 201 when the metal layer 203 is formed on the top surface of the graphene layer 202 through the heat pressing process or the ohmic contact metal layer 206 is formed on the top surface of the light emitting diode unit 205 through the heat treatment process. Phosphorus gold (Au) is diffused into the metal layer 203 and combined with silver (Ag), which is a reflective layer of the light emitting diode unit 205. The graphene layer 202 prevents diffusion of gold ions, thereby combining gold ions with silver. To prevent

Furthermore, the bonding layer 201, the graphene layer 202, and the metal layer 203 are repeatedly formed in plural to protect the metal layer 203. The present invention is not limited thereto, and the metal layer 203 may be made of an n-ohmic contact metal, and the ohmic contact metal layer 206 formed on the upper surface of the light emitting diode unit 205 may be made of a p-omic contact metal.

6B includes a substrate 204, a gate insulating layer 207, a bonding layer 201, a graphene layer 202, and a metal layer 203. In one embodiment, the bonding layer 201 includes a polysilicon film, and the metal layer 203 includes tungsten having a low resistivity value.

Furthermore, the graphene layer 202 prevents the diffusion of metal from the metal layer 203 to the bonding layer 201 during the thermal process after the metal layer 203 is formed, thereby preventing the metal ions and the bonding layer (diffused from the metal layer 203). The polysilicon film of 201 is bonded to prevent the reaction of generating the metal silicide and reduces the volume expansion and the stress generation of the semiconductor device 501.

Furthermore, the graphene layer 202 has an ohmic contact with the metal layer 203, thereby lowering the interface resistance between the graphene layer 202 and the metal layer 203, and the schottky contact with the bonding layer 201. (Schottky Contact) is formed, the bonding energy between the graphene layer 202 and the bonding layer 201 increases.

In addition, the electronic device 200 according to the present invention is not limited thereto, and may be an electronic device, an optoelectronic device, an optical device, a light emitting device, an organic light emitting device, an organic semiconductor device, a display device, a solar device, a thin film sensor, a metal wiring device. Or in bio-devices.

Terms used throughout the present specification are terms defined in consideration of functions in the embodiments of the present invention, and may be sufficiently modified according to the intention, management, or the like of a user or an operator. It should be made based on the contents.

As described above, the present invention is not limited to the above-described embodiment and the accompanying drawings, and various forms of substitution, modification, and change are possible without departing from the technical spirit of the present invention described in the claims. It will be apparent to those of ordinary skill in the art.

100: light emitting diode element 101: semiconductor element
102 substrate 103 bonding layer
104: diffusion barrier film 105: p-omic junction metal layer
106: light emitting diode portion 107: n-omic junction metal layer
108: gate insulating film 109: polysilicon layer
110: titanium film 111: tungsten nitride film
112: tungsten layer 113: titanium layer
114: titanium nitride layer 115: amorphous film
200: electronic device 201: bonding layer
202: graphene layer 203: metal layer

Claims (15)

A metal layer made of a single metal or an alloy;
A graphene layer formed on the bottom surface of the metal layer; And
A bonding layer formed on the bottom surface of the graphene layer;
Electronic device provided with a graphene layer for preventing metal diffusion comprising a.
The electronic device of claim 1, wherein the electronic device includes the metal diffusion barrier layer.
When m bonding layers and m metal layers are repeatedly formed on the metal layer, m-1 graphene layers are formed between the bonding layer and the metal layer. Electronic devices.
The electronic device of claim 1, wherein the electronic device includes the metal diffusion barrier layer.
When m bonding layers and m metal layers are repeatedly formed on the metal layer, m graphene layers are formed between the bonding layer and the metal layer. .
The electronic device according to claim 2 or 3, wherein the graphene layer for preventing metal diffusion is provided.
Electronic device provided with a graphene layer for preventing metal diffusion, characterized in that the m or m-1 of the graphene layer all the same thickness.
The electronic device according to any one of claims 2 and 3, wherein the graphene layer for preventing metal diffusion is provided.
At least one or more thicknesses of m or m-1 graphene layers are different.
The method of claim 1, wherein the graphene layer,
An electronic device with a graphene layer for preventing metal diffusion, which is formed of a two-dimensional planar structure made of graphite or a structure doped with heterogeneous atoms in graphite.
The method of claim 1, wherein the graphene layer,
Electronic device with a graphene layer for preventing metal diffusion, characterized in that the thickness is 0.2nm to 1.5㎛.
The method of claim 1, The bonding layer,
An electronic device with a graphene layer for preventing metal diffusion, which is formed of at least one of a single metal film, an alloy film, an oxide film, an organic film, and an inorganic film.
The electronic device of claim 1, wherein the metal diffusion preventing graphene layer is provided.
For preventing metal diffusion, which is applied to any one or more of electronic devices, optoelectronic devices, optical devices, light emitting devices, organic light emitting devices, organic semiconductor devices, display devices, solar devices, thin film sensors, metal wiring devices or bio devices. Electronic device with a graphene layer.
Forming a graphene layer made of carbon on the bonding layer;
Forming a metal layer on an upper surface of the graphene layer;
Electronic device manufacturing method provided with a graphene layer for preventing metal diffusion, comprising a.
The electronic device manufacturing method of claim 10, wherein the metal diffusion prevention graphene layer is provided.
When m bonding layers and m metal layers are repeatedly formed on the metal layer, m-1 graphene layers are formed between the bonding layer and the metal layer. Electronic device manufacturing method.
The electronic device manufacturing method of claim 10, wherein the metal diffusion prevention graphene layer is provided.
When m bonding layers and m metal layers are repeatedly formed on the metal layer, m graphene layers are formed between the bonding layer and the metal layer. Manufacturing method.
The method of claim 11, wherein the graphene layer for preventing metal diffusion is provided.
Method of manufacturing an electronic device provided with a graphene layer for preventing metal diffusion, characterized in that the m or m-1 of the graphene layer all the same thickness.
The method of claim 11, wherein the graphene layer for preventing metal diffusion is provided.
The method of manufacturing an electronic device with a graphene layer for preventing metal diffusion, wherein at least one of m or m-1 graphene layers is different in thickness.
The method of claim 10, wherein the graphene layer,
Thermal Evaportor, Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), Sputtering, Co-Evaporation, Spin Coating, Doctor Blade, Spraying Coating, Screen Printing, Ink-Jet printing, Pad Printing, Gravure Printing, Lithography Printing ), A roll-to-roll (R2R) or a method for producing an electronic device with a graphene layer for preventing metal diffusion, characterized in that formed in any one or more of the method.

Images