KR20110115814A - Etchant and method for preparing electronic device - Google Patents

Abstract

An etching solution for selectively etching both the doped semiconductor layer and the metal electrode layer sequentially disposed on the intrinsic semiconductor layer of the electronic device with respect to the intrinsic semiconductor layer, the metal electrode etching component; Transition metals and / or transition metal salts; And inorganic salts including hydrofluoric acid and / or fluorine.

Description

Etching liquid and electronic device manufacturing method {Etchant and method for preparing electronic device}

An etchant and an electronic device manufacturing method using the etchant are provided.

A thin film transistor, which is a kind of electronic device, is used as a switching element in a flat panel display such as a liquid crystal display or an organic light emitting display. The thin film transistor may have, for example, a structure shown in FIG. 1F. In FIG. 1E, the gate electrode 2 is disposed on the insulating substrate 10, the gate insulating layer 3 is disposed on the gate electrode 2, and generally undoped intrinsic on the gate insulating layer 3. A channel layer 4, which is a semiconductor layer, is disposed, and ohmic contact layers 5a, 5b, which are generally doped semiconductor layers, are disposed on the channel layer 4, and on the ohmic contact layers 5a, 5b. Drain / source electrodes 6a and 6b are disposed.

In the conventional etching process, the spaced drain / source electrodes 6a and 6b and the spaced apart ohmic contact layers 5a and 5b of FIG. 1E sequentially etch the electrode layer 6 and the ohmic contact layer 5 in FIG. 1D. Is obtained. Wet etching is used to etch the electrode layer 6, and dry etching is used to etch the ohmic contact layer 5. Therefore, the manufacturing process is complicated. In addition, the conventional etching solution exhibited higher etching performance on the gate insulating layer 3, the insulating substrate 10, and the channel layer 4 than the ohmic contact layer 5.

Therefore, the etching process of the electrode layer 6 and the ohmic contact layer 5 could not be simplified.

One aspect of the present invention is to provide an etchant having a new composition.

Another aspect of the present invention to provide an electronic device manufacturing method using the etchant.

According to one aspect of the invention

An etching solution for selectively etching both the doped semiconductor layer and the metal electrode layer sequentially disposed on the intrinsic semiconductor layer of the electronic device with respect to the intrinsic semiconductor layer,

The metal electrode etching component;

Transition metals, transition metal salts or mixtures thereof; And

An etchant comprising; hydrofluoric acid, an inorganic salt containing fluorine, or a mixture thereof.

According to another aspect of the invention,

A method of manufacturing an electronic device comprising selectively etching both a doped semiconductor layer and a metal electrode layer sequentially disposed on an intrinsic semiconductor layer of an electronic device with respect to the intrinsic semiconductor layer, wherein the etchant used in the etching step is

The metal electrode etching component;

Transition metals, transition metal salts or mixtures thereof; And

Provided are an electronic device manufacturing method including hydrofluoric acid, an inorganic salt containing fluorine, or a mixture thereof.

The etching solution according to an aspect of the present invention simplifies and manufactures an electronic device manufacturing process by selectively etching both the doped semiconductor layer and the metal electrode layer sequentially disposed on the intrinsic semiconductor layer of the electronic device with respect to the intrinsic semiconductor layer. Increasing process efficiency, reducing production costs, and / or improving the performance of electronic devices.

1A to 1E are cross-sectional views illustrating a thin film transistor manufacturing process according to an exemplary embodiment.
2 to 11 are scanning electron micrographs of the thin film transistors after etching with the etchant of Examples 1 to 10, respectively.
12 is a scanning electron micrograph of a thin film transistor after etching with an etchant of 1 in comparison.
<Explanation of symbols for the main parts of the drawings>
2… Gate electrode 3.. Insulation film
4… Intrinsic semiconductor layer (channel layer) 5, 5a, 5b... Doped semiconductor layer (Omic contact layer)
6... Metal layer 10... Insulation Board
6a, 6b..source / drain electrodes

Hereinafter, an etching solution and an electronic device manufacturing method using the etching solution according to an exemplary embodiment will be described in more detail.

An etchant according to an exemplary embodiment is an etchant for selectively etching both the doped semiconductor layer and the metal electrode layer sequentially disposed on the intrinsic semiconductor layer of the electronic device with respect to the intrinsic semiconductor layer, wherein the metal electrode etching component; Transition metals, transition metal salts or mixtures thereof; And inorganic salts or mixtures thereof including hydrofluoric acid and fluorine.

In the etchant, the metal electrode etching component serves to etch the metal electrode. In addition, the transition metal ion derived from the transition metal or a salt of the transition metal in the etching solution serves to selectively improve the etching rate for the doped semiconductor layer. Therefore, only the doped semiconductor layer may be selectively etched while suppressing etching of the intrinsic semiconductor layer.

Accordingly, the etchant may selectively collectively etch only the metal electrode layer and the doped semiconductor layer while minimizing the etching of other layers such as the insulating layer and the insulating substrate included in the electronic device.

In contrast, when using a conventional etching solution including the metal electrode etching component and hydrofluoric acid or fluorine without the transition metal or the transition metal salt, the doped semiconductor layer is hardly etched, and only the electrode layer is etched. In addition, an electrode insulating layer, an insulating substrate, etc. may be etched by the conventional etchant.

For example, the content of the metal electrode etching component in the etching solution may be 0.1 to 99.90% by weight based on the total weight of the etching solution. For example, the content of the metal electrode etching component may be 1 to 99% by weight based on the total weight of the etching solution. For example, the content of the metal electrode etching component may be 1 to 98% by weight based on the total weight of the etching solution.

For example, the content of the transition metal, the transition metal salt, or a mixture thereof in the etching solution may be 0.005 to 30% by weight based on the total weight of the etching solution. For example, the content of the transition metal, the transition metal salt or a mixture thereof may be 0.005 to 20% by weight based on the total weight of the etching solution. For example, the content of the transition metal, the transition metal salt or a mixture thereof may be 0.005 to 10% by weight based on the total weight of the etching solution.

For example, the content of the inorganic salt containing hydrofluoric acid and fluorine or a mixture thereof in the etching solution may be 0.05 to 30% by weight based on the total weight of the etching solution. For example, the content of the hydrofluoric acid, an inorganic salt containing fluorine, or a mixture thereof may be 0.05 to 20% by weight based on the total weight of the etching solution. For example, the amount of the hydrofluoric acid, an inorganic salt including fluorine, or a mixture thereof may be 0.05 to 10 wt% based on the total weight of the etching solution.

For example, the etching solution may include 0.1 to 99.90 wt% of the metal electrode etching component; 0.005 to 30% by weight of the transition metal, the transition metal salt or a mixture thereof; 0.05 to 30% by weight of the inorganic salt including hydrofluoric acid and fluorine or mixtures thereof; And it may include 0.045 to 99% by weight of water, but is not necessarily limited to this composition, the content of each component can be appropriately modified within the range in which the doped semiconductor layer and the metal electrode can be selectively etched at the same time In the etching solution, the metal electrode etching component may be at least one selected from the group consisting of hydrogen peroxide, inorganic acid, inorganic acid salt, organic acid, organic acid salt, chlorine compound, and ferric salt.

The inorganic acid may be, but is not limited to, phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, sulfamic acid, perchloric acid, chromic acid, sulfurous acid, nitrous acid, and the like, and may be used in the art as an inorganic acid capable of etching a metal electrode. Anything you can use is available.

The inorganic acid salt may be, for example, an alkali metal salt of phosphoric acid, an alkali metal salt of sulfuric acid, an alkali metal salt of nitric acid, an alkali metal salt of hydrochloric acid, and the like, but is not limited thereto, and may etch a metal electrode. Any inorganic acid salt may be used as long as it can be used in the art. The inorganic acid salt may be used together with the inorganic acid to form a buffer solution.

For example, the inorganic acid salt is KHSO ₄ , K ₂ S ₂ O ₈ , (NH ₄ ) ₂ SO ₄ , (NH ₄ ) ₂ S ₂ O ₈ , Na ₂ SO ₄ , NaHSO ₄ , AlNH ₄ (SO ₄ ) ₂ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , CaSO ₄ , Li ₂ SO ₄ , MgSO ₄ , KNO ₃ , NH ₄ NO ₃ , Ca (NO ₃ ) ₂ , NaNO ₃ , Ba (NO ₃ ) ₂ ), LiNO ₃ , Mg (NO ₃ ) ₂ , KNO ₃ , NH ₄ NO ₃ , CH ₃ COOK, and the like.

The organic acid may be formic acid, acetic acid, oxalic acid, propionic acid, glycolic acid, tartaric acid, citric acid, and the like, but is not limited thereto. Any organic acid capable of etching a metal electrode may be used as long as it can be used in the art. It is possible.

The organic acid salt may be, for example, an alkali metal salt of formic acid, an alkali metal salt of acetic acid, and the like, but is not limited thereto, and may be used in the art as an organic acid salt capable of etching a metal electrode. All of them are available. The organic acid salt may be used together with the organic acid to form a buffer solution.

The chlorine-based compound as a compound containing chlorine, for example, KCl, HCl, LiCl, NH ₄ Cl, CuCl ₂ , FeCl ₂ , CaCl ₂ , CoCl ₂ , NiCl ₂ , ZnCl ₂ , AlCl ₃ , BaCl ₂ , BeCl ₂ , BiCl ₃ , CdCl ₂ , CeCl ₂ , CsCl ₂ , H ₂ PtCl ₆ , CrCl _{3 and the} like, but is not limited to these, as long as it can be used in the art as a chlorine-based compound capable of etching the metal electrode All are available.

Ferric salt is a salt of ferric Fe (III), for example, FeCl ₃ , Fe (NO ₃ ) ₃ , Fe ₂ (SO ₄ ) ₃ , Fe ₂ O _3, etc. However, the present invention is not limited thereto, and any ferric salt capable of etching the metal electrode may be used as long as it can be used in the art.

The transition metal in the etchant is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta It may be at least one selected from the group consisting of, W, Re, Os, Ir, Pt, Au, Hg, lanthanide elements, and actinides. For example, the transition metal may be Cu.

The transition metal salt in the etchant is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta It may be a transition metal salt containing ions of at least one metal selected from the group consisting of W, Re, Os, Ir, Pt, Au, Hg, lanthanide elements, and actinium elements.

In the etchant, the transition metal salt is CuSO ₄ , Cu (NO ₃ ) ₂ , CuO, (CH ₃ CO ₂ ) ₂ Cu, Copper Gluconate, CuCl, CuCl ₂ , CuF ₂ , Cu (OH) ₂ , Cu ₂ S, Fe (NO ₃ ) ₃ , FeSO ₄ , Ni (NO ₃ ) ₂ , NiSO ₄ , AgNO ₃ , Ag ₂ SO ₄ , (CH ₃ CO ₂ ) ₂ Co, (CH ₃ CO ₂ ) ₂ Pd, Pd (NO _{3) 2,} may be at least one member selected from the group consisting of such as _{Rh (CH 3 CO 2) 2} , Rh 2 O 3. For example, the transition metal salt may be CuSO ₄ .

The inorganic salt containing fluorine in the etchant is KF, LiF, NaF, RbF, CsF, MgF ₂ , NH ₄ F, H ₂ SiF ₆ , NaHF ₂ , NH ₄ F, NH ₄ HF ₂ , NH ₄ BF ₄ , It may be one or more selected from the group consisting of KHF ₂ , AlF ₃ , HBF ₄ and the like. The inorganic salt containing fluorine may be used in admixture with hydrofluoric acid.

For example, the etchant may include 5 to 30% by weight of H ₂ O ₂ , 0.01 to 10% by weight of CuSO ₄ , 0.05 to 10% by weight of HF, and 50 to 94.94% by weight of water.

The etchant is a conventional metal electrode etching solution, a transition metal, a transition metal salt or a mixture thereof; And hydrofluoric acid, inorganic salts including fluorine, or mixtures thereof. For example, it may be prepared by adding CuSO ₄ and HF to the hydrogen peroxide-based etching solution. The metal etching solution is an etching solution containing the above-described etching component for the metal electrode.

In the electronic device manufactured using the etchant, the intrinsic semiconductor layer may be amorphous silicon. In addition, the doped semiconductor layer may be amorphous silicon doped with an n-type dopant. For example, the doped semiconductor layer may be n + amorphous silicon (n + a-Si: H). The n-type dopant may be a Periodic Table 5A element having more outermost electrons than silicon. For example, it may be P, N, As, Sb, and the like. The content of the n-type dopant may be less than 50 mol%. The metal electrode layer may be made of molybdenum.

The electronic device manufactured using the etchant may be a thin film transistor, but is not necessarily limited to the thin film transistor, and any electronic device that may be used in the art may be used.

The thin film transistor may have, for example, a structure of FIG. 1E. In FIG. 1E, the insulating substrate 10 may be glass, but is not necessarily limited to glass, and may be used as long as the insulating substrate 10 may be used as a substrate in the art, such as polycarbonate and quartz. In FIG. 1E, the gate electrode 2 may be a conductive metal such as molybdenum, aluminum, or niobium, but is not necessarily limited to a metal and may be used as long as it can be used as an electrode material in the art. In FIG. 1E, the gate insulating layer 3 may be silicon nitride (SiNx), but the gate insulating layer 3 is not limited thereto, and any gate insulating layer 3 may be used as the insulating layer of the gate electrode in the art. In FIG. 1E, the semiconductor layer 4 may be amorphous silicon as an undoped intrinsic semiconductor layer, but any semiconductor that is not necessarily limited to amorphous silicon may be used as long as it can be used as an intrinsic semiconductor layer in the art. In FIG. 1E, the semiconductor layer 4 serves as a channel layer in the thin film transistor. In FIG. 1E, the ohmic contact layers 5a and 5b may be n + amorphous silicon as a semiconductor layer doped with an n-type dopant, but are not limited thereto, and may serve as an ohmic contact layer in the art. All ramen can be used.

An electronic device manufacturing method according to another aspect of the present invention includes the step of selectively etching both the doped semiconductor layer and the metal electrode layer sequentially disposed on the intrinsic semiconductor layer of the electronic device with respect to the intrinsic semiconductor layer As the manufacturing method, the etching liquid used in the etching step is the metal electrode etching component; Transition metals, transition metal salts or mixtures thereof; And inorganic salts or mixtures thereof including hydrofluoric acid and fluorine.

For example, the etching solution used in the manufacturing method is 0.1 to 99.90% by weight of the metal electrode etching component; 0.005 to 30% by weight of the transition metal, the transition metal salt or a mixture thereof; 0.05 to 30% by weight of the inorganic salt including hydrofluoric acid and fluorine or mixtures thereof; And it may include 0.045 to 99% by weight of water, but is not necessarily limited to this composition, the content of each component can be appropriately modified within the range in which the doped semiconductor layer and the metal electrode can be selectively etched at the same time have.

In the manufacturing method, the metal electrode etching component may be at least one selected from the group consisting of hydrogen peroxide, inorganic acid, inorganic acid salt, organic acid, organic acid salt, chlorine compound, and ferric salt.

The inorganic acid may be, but is not limited to, phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, sulfamic acid, perchloric acid, chromic acid, sulfurous acid, nitrous acid, and the like, and may be used in the art as an inorganic acid capable of etching a metal electrode. Anything you can use is available.

The inorganic acid salt may be, for example, an alkali metal salt of phosphoric acid, an alkali metal salt of sulfuric acid, an alkali metal salt of nitric acid, an alkali metal salt of hydrochloric acid, and the like, but is not limited thereto, and may etch a metal electrode. Any inorganic acid salt may be used as long as it can be used in the art. The inorganic acid salt may be used together with the inorganic acid to form a buffer solution.

For example, the inorganic acid salt is KHSO ₄ , K ₂ S ₂ O ₈ , (NH ₄ ) ₂ SO ₄ , (NH ₄ ) ₂ S ₂ O ₈ , Na ₂ SO ₄ , NaHSO ₄ , AlNH ₄ (SO ₄ ) ₂ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , CaSO ₄ , Li ₂ SO ₄ , MgSO ₄ , KNO ₃ , NH ₄ NO ₃ , Ca (NO ₃ ) ₂ , NaNO ₃ , Ba (NO ₃ ) ₂ ), LiNO ₃ , Mg (NO ₃ ) ₂ , KNO ₃ , NH ₄ NO ₃ , CH ₃ COOK, and the like.

The organic acid may be formic acid, acetic acid, oxalic acid, propionic acid, glycolic acid, tartaric acid, citric acid, and the like, but is not limited thereto. Any organic acid capable of etching a metal electrode may be used as long as it can be used in the art. It is possible.

The organic acid salt is a metal salt of the organic acids, for example, alkali metal salt of formic acid, alkali metal salt of acetic acid,... And the like, but are not necessarily limited thereto, and any organic acid salt capable of etching the metal electrode may be used as long as it can be used in the art. The organic acid salt may be used together with the organic acid to form a buffer solution.

The chlorine-based compound as a compound containing chlorine, for example, KCl, HCl, LiCl, NH ₄ Cl, CuCl ₂ , FeCl ₂ , CaCl ₂ , CoCl ₂ , NiCl ₂ , ZnCl ₂ , AlCl ₃ , BaCl ₂ , BeCl ₂ , BiCl ₃ , CdCl ₂ , CeCl ₂ , CsCl ₂ , H ₂ PtCl ₆ , CrCl _{3 and the} like, but is not limited to these, as long as it can be used in the art as a chlorine-based compound capable of etching the metal electrode All are available.

Ferric salt is a salt of ferric Fe (III), for example, FeCl ₃ , Fe (NO ₃ ) ₃ , Fe ₂ (SO ₄ ) ₃ , Fe ₂ O _3, etc. However, the present invention is not limited thereto, and any ferric salt capable of etching the metal electrode may be used as long as it can be used in the art.

In the etching solution used in the preparation method, the transition metal is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, It may be at least one selected from the group consisting of Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, lanthanide elements, and actinides. For example, the transition metal may be Cu.

In the etchant used in the preparation method, the transition metal salt is CuSO ₄ , Cu (NO ₃ ) ₂ , CuO, (CH ₃ CO ₂ ) ₂ Cu, Copper Gluconate, CuCl, CuCl ₂ , CuF ₂ , Cu (OH) ₂ , Cu ₂ S, Fe (NO ₃ ) ₃ , FeSO ₄ , Ni (NO ₃ ) ₂ , NiSO ₄ , AgNO ₃ , Ag ₂ SO ₄ , (CH ₃ CO ₂ ) ₂ Co, (CH ₃ CO ₂ ) ₂ Pd, Pd (NO ₃ ) _{2 It} may be one or more selected from the group consisting of Rh (CH ₃ CO ₂ ) ₂ , Rh ₂ O ₃ and the like. For example, the transition metal salt may be CuSO ₄ .

In the etching solution used in the preparation method, the inorganic salt containing fluorine is KF, LiF, NaF, RbF, CsF, NH ₄ F, H ₂ SiF ₆ , NaHF ₂ , NH ₄ F, NH ₄ HF ₂ , NH ₄ BF ₄ , KHF ₂ , AlF ₃ , HBF ₄ , etc. may be one or more selected from the group consisting of, and may be used in combination with hydrofluoric acid.

For example, the etching solution used in the preparation method may include 5 to 30% by weight of H ₂ O ₂ , 0.01 to 10% by weight of CuSO ₄ , 0.05 to 10% by weight of HF, and 50 to 94.94% by weight of water.

In the electronic device manufacturing method, the intrinsic semiconductor layer may be amorphous silicon. In addition, the doped semiconductor layer may be amorphous silicon doped with an n-type dopant. For example, the doped semiconductor layer may be n + amorphous silicon (n + a-Si: H). The n-type dopant may be a Periodic Table 5A element having more outermost electrons than silicon. For example, it may be N, P, As, Sb and the like. The content of the n-type dopant may be less than 50 mol%. The metal electrode layer may be made of molybdenum.

The electronic device manufactured by the electronic device manufacturing method may be a thin film transistor, but is not necessarily limited to the thin film transistor, and any electronic device that may be used in the art may be used.

A method of manufacturing a thin film transistor, which is an example of the electronic device, may include disposing a gate electrode on an insulating substrate before the etching step; And sequentially disposing an insulating layer, an intrinsic semiconductor layer, a doped semiconductor layer, and a metal electrode layer on the gate electrode.

The step of disposing a gate electrode on the insulating substrate may be performed by forming a metal film on the insulating substrate and then etching the metal film.

The sequentially disposing the insulating layer, the intrinsic semiconductor layer, the doped semiconductor layer, and the metal electrode layer on the gate electrode may be performed by forming the layers sequentially by sputtering, chemical vapor deposition, physical vapor deposition, or the like. Can be.

An embodiment of a method of manufacturing the thin film transistor will be described with reference to FIGS. 1A through 1E.

As shown in FIG. 1, a metal film 2 is first formed on an insulating substrate 10. The metal film 2 may be an alloy and multiple layers or more. The metal film 2 may be formed by sputtering.

Subsequently, a photoresist film is formed on the entire region of the insulating substrate 10, and then the exposure, development, and etching processes are performed to form the gate electrode 2 as shown in FIG. 1B. A gate line and a gate pad connected to the gate electrode 2 are also formed at the same time, but are not shown in the drawing.

After the gate electrode is formed, as shown in FIG. 1C, the gate insulating layer 3, the intrinsic semiconductor layer 4, and the doped semiconductor layer 5 are sequentially formed in the entire region of the insulating substrate 10. Subsequently, the channel layer 4 is formed on the gate electrode by etching according to a photolithography process. The doped semiconductor layer 5 remains on the channel layer 4.

Subsequently, a metal film 6 is deposited on the doped semiconductor layer 5 as shown in FIG. 1D. A protective layer having a predetermined pattern is additionally formed on the metal film 6, but is not formed in the drawing.

Subsequently, as shown in FIG. 1E, both the metal film 6 and the doped semiconductor layer 5 are selectively wet-etched with respect to the intrinsic semiconductor layer 4 using the above-described etching solution to form the intrinsic semiconductor layer 4. To be exposed. At the same time, spaced source / drain electrodes 6a and 6b and doped semiconductor layers 5a and 5b are formed.

The present invention will be described in more detail with reference to the following Examples. The configuration shown in the following examples are only for the purpose of understanding the invention to the extent that it is not intended to limit the technical scope of the present invention to the embodiments presented in the examples in any case.

(Etch Composition)

Example 1 and Comparative Example 1

The etchant of Examples 1 to 4 and Comparative Example 1 according to the etchant composition of the present invention was prepared as shown in Table 1 below. The compositions of Examples 1 to 4 and Comparative Example 1 are shown in Table 1. In Table 1 below, the metal electrode etching component is referred to as a first component, the transition metal, a transition metal salt or a mixture thereof is referred to as a second component, and an inorganic salt containing hydrofluoric acid and fluorine or a mixture thereof is referred to as a third component.

The first component used in Example 1 is H ₂ O ₂ , the second component is copper metal, and the third component is HF.

The first component used in Example 2 is H ₂ O ₂ , the second component is CuSO ₄ , and the third component is HF.

The first component used in Example 3 is H ₂ O ₂ , the second component is Cu (NO ₃ ) ₂ , and the third component is HF.

The first component used in Example 4 is H ₂ O ₂ , the second component is CuO and the third component is HF.

The first component used in Example 5 is H ₂ O ₂ , the second component is (CH ₃ CO ₂ ) ₂ Cu, and the third component is HF.

The first component used in Example 6 is H ₂ O ₂ , the second component is CuCl ₂ , and the third component is HF.

The first component used in Example 7 is H ₂ O ₂ , the second component is AgNO ₃ , and the third component is HF.

The first component used in Example 8 is H ₂ O ₂ , the second component is Rh (CH ₃ CO ₂ ) ₂ , and the third component is HF.

The first component used in Example 9 is H ₂ O ₂ , the second component is CuSO ₄ , and the third component is NH ₄ F.

The first component used in Example 10 is H ₂ O ₂ , the second component is CuSO ₄ , and the third component is KF.

The first component used in Comparative Example 1 is H ₂ O ₂ .

ingredient 1st component
[weight%] 2nd component
[weight%] Third component
[weight%] water
[weight%] Example 1 20 0.1 0.3 79.6 Example 2 20 0.1 0.3 79.6 Example 3 20 0.1 0.3 79.6 Example 4 20 0.1 0.3 79.6 Example 5 20 0.1 0.3 79.6 Example 6 20 0.1 0.3 79.6 Example 7 20 0.2 0.3 79.5 Example 8 20 0.2 0.3 79.5 Example 9 20 0.1 0.8 79.1 Example 10 20 0.1 0.8 79.1 Comparative Example 1 20 0 0 80

Evaluation Example 1 Evaluation of Etching Ability of Etching Liquid

A thin film transistor having the structure of FIG. 1D was prepared. The insulating substrate is glass, the insulating film is silicon nitride (SiNx), the intrinsic semiconductor layer is amorphous silicon, the doped semiconductor layer is n + amorphous silicon, and the source / drain electrodes are copper layers.

The thin film transistors are etched using the etchant of Examples 1 to 10 and the etchant of Comparative Example 1 are shown in FIGS. 2 to 11 and 12, respectively.

2 is a scanning electron micrograph of a thin film transistor after etching using the etchant of Example 1, Figure 12 is a scanning electron micrograph of a thin film transistor after etching using the etchant of Comparative Example 1.

As shown in FIG. 2, when the etchant of Example 1 was used, only the metal electrode layer and n + amorphous silicon were selectively etched to expose the amorphous silicon layer.

In contrast, when the etchant of Comparative Example 1 was used as shown in FIG. 12, only the metal electrode layer was etched, the n + amorphous silicon layer was maintained as it was, and the insulating film was etched instead.

Therefore, the etching solution of Example 1 has significantly improved selectivity to the intrinsic semiconductor layer compared to Comparative Example 1. In addition, the etching solution of Example 1 may be a batch etching of the metal electrode layer and the doped semiconductor layer.

In addition, as shown in FIGS. 3 to 11, the etching solutions of Examples 2 to 10 also significantly improved selectivity compared to Comparative Example 1.

Claims (21)

An etching solution for selectively etching both the doped semiconductor layer and the metal electrode layer sequentially disposed on the intrinsic semiconductor layer of the electronic device with respect to the intrinsic semiconductor layer,
The metal electrode etching component;
Transition metals, transition metal salts or mixtures thereof; And
An etchant comprising hydrofluoric acid, an inorganic salt containing fluorine, or a mixture thereof. The method of claim 1, wherein the etchant
0.1 to 99.90 wt% of the metal electrode etching component;
0.005 to 30% by weight of the transition metal, the transition metal salt or a mixture thereof;
0.05 to 30% by weight of the inorganic salt including hydrofluoric acid and fluorine or mixtures thereof; And
Etch liquid containing a residual amount of water. The etchant according to claim 1, wherein the metal electrode etching component is at least one selected from the group consisting of hydrogen peroxide, inorganic acid, inorganic acid salt, organic acid, organic acid salt, chlorine compound, and ferric salt. The method of claim 1, wherein the transition metal is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, At least one etchant selected from the group consisting of Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, lanthanide elements, and actinium elements. The method of claim 1, wherein the transition metal salt is CuSO ₄ , Cu (NO ₃ ) ₂ , CuO, (CH ₃ CO ₂ ) ₂ Cu, Copper Gluconate, CuCl, CuCl ₂ , CuF ₂ , Cu (OH ) ₂ , Cu ₂ S, Fe (NO ₃ ) ₃ , FeSO ₄ , Ni (NO ₃ ) ₂ , NiSO ₄ , AgNO ₃ , Ag ₂ SO ₄ , (CH ₃ CO ₂ ) ₂ Co, (CH ₃ CO ₂ ) ₂ Pd, Pd (NO ₃ ) ₂ , Rh (CH ₃ CO ₂ ) ₂ , Rh ₂ O _{3 And the} etchant at least one selected from the group consisting of. According to claim 1, wherein the inorganic salt containing fluorine is KF, LiF, NaF, RbF, CsF, NH ₄ F, H ₂ SiF ₆ , NaHF ₂ , NH ₄ F, NH ₄ HF ₂ , NH ₄ BF ₄ , Etching liquid of at least one selected from the group consisting of KHF ₂ , AlF ₃ , HBF ₄ . The etchant according to claim 1, comprising 5 to 30% by weight of H ₂ O ₂ , 0.01 to 10% by weight of CuSO ₄ , 0.05 to 10% by weight of HF, and a balance of water. The etchant of claim 1, wherein the intrinsic semiconductor layer is amorphous silicon. The etchant of claim 1, wherein the doped semiconductor layer is amorphous silicon doped with an n-type dopant. The etchant of claim 1, wherein the electronic device is a thin film transistor. A method of manufacturing an electronic device comprising selectively etching both a doped semiconductor layer and a metal electrode layer sequentially disposed on an intrinsic semiconductor layer of an electronic device with respect to the intrinsic semiconductor layer, wherein the etchant used in the etching step is
The metal electrode etching component;
Transition metals, transition metal salts or mixtures thereof; And
Fluoric acid, inorganic salts containing fluorine or a mixture thereof; manufacturing method of an electronic device comprising a. The method of claim 11, wherein the etchant
0.1 to 99.90 wt% of the metal electrode etching component;
0.005 to 30% by weight of the transition metal, the transition metal salt or a mixture thereof;
0.05 to 30% by weight of the inorganic salt including hydrofluoric acid and fluorine or mixtures thereof; And
Electronic device manufacturing method comprising a residual amount of water. The etchant according to claim 11, wherein the metal electrode etching component is at least one selected from the group consisting of hydrogen peroxide, inorganic acid, inorganic acid salt, organic acid, organic acid salt, chlorine compound, and ferric salt. The method of claim 11, wherein the transition metal is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lanthanide Aid, Actinium group element is at least one selected from the group consisting of electronic device manufacturing method. The method of claim 11, wherein the transition metal salt is CuSO ₄ , Cu (NO ₃ ) ₂ , CuO, (CH ₃ CO ₂ ) ₂ Cu, Copper Gluconate, CuCl, CuCl ₂ , CuF ₂ , Cu (OH ) ₂ , Cu ₂ S, Fe (NO ₃ ) ₃ , FeSO ₄ , Ni (NO ₃ ) ₂ , NiSO ₄ , AgNO ₃ , Ag ₂ SO ₄ , (CH ₃ CO ₂ ) ₂ Co, (CH ₃ CO ₂ ) _At least one selected from the group consisting of ₂ Pd, Pd (NO ₃ ) ₂ , Rh (CH ₃ CO ₂ ) ₂ , Rh ₂ O ₃ , and the like. Electronic device manufacturing method. The method according to claim 11, wherein the inorganic salt containing fluorine is KF, LiF, NaF, RbF, CsF, NH ₄ F, H ₂ SiF ₆ , NaHF ₂ , NH ₄ F, NH ₄ HF ₂ , NH ₄ BF ₄ , KHF ₂ , AlF ₃ , HBF _{4 An} electronic device manufacturing method of at least one selected from the group consisting of. The method of claim 11, comprising 5 to 30% by weight of H ₂ O ₂ , 0.01 to 10% by weight of CuSO ₄ , 0.05 to 10% by weight of HF, and a balance of water. The method of claim 11, wherein the intrinsic semiconductor layer is amorphous silicon. The method of claim 11, wherein the doped semiconductor layer is amorphous silicon doped with an n-type dopant. The method of claim 11, wherein the electronic device is a thin film transistor. The method of claim 20, wherein before the etching step
Disposing a gate electrode on the insulating substrate; And
And sequentially disposing an insulating layer, an intrinsic semiconductor layer, a doped semiconductor layer, and a metal electrode layer on the gate electrode.

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