KR101819367B1 - Fe-Ni ALLOY FOIL AND METHOD FOR MANUFACTURING THEREOF - Google Patents

Abstract

The present invention relates to Fe-Ni alloy foil and, more specifically, relates to Fe-Ni alloy foil and a method for manufacturing the same, wherein the Fe-Ni alloy foil is appropriate for an organic light emitting diode material. The Fe-Ni alloy foil comprises: 36-45 wt% of Ni; and the remainder consisting of Fe and inevitable impurities.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a Fe-Ni alloy foil,

The present invention relates to an iron-nickel alloy foil, and more particularly, to an iron-nickel alloy foil suitable for an organic light emitting diode (OLED) material and a method of manufacturing the same.

Organic light emitting diodes (OLEDs) are emerging as next-generation displays that can replace LCDs (liquid crystal displays) in the display market.

OLEDs have the advantage that they emit light and colors themselves, can control the amount of light, consume less power, respond quickly, and have few afterimages. Also, the color is rich and bright, and the viewing angle is wide.

With these advantages, OLED display industry is focusing on automobile, mobile and TV market recently.

The fabrication of full color devices consisting of RGB sub-pixels used in the manufacture of OLED displays takes place in high temperature deposition equipment. The deposition apparatus is composed of a substrate, a deposition mask, a frame, and the like. As the deposition process is performed at a high temperature, the deposition apparatus is affected by temperature, and a positional difference occurs due to a dimensional change due to a thermal expansion coefficient. Therefore, there is a problem that the position and dimensional accuracy of the evaporation material adhered on the substrate is lowered. Therefore, in order to precisely control the position of the mask, prevent thermal expansion, and satisfy the accuracy of the mask and the substrate, it is essential to select the mask and the frame material at the same level as the coefficient of thermal expansion of the substrate.

On the other hand, as the material of the deposition mask, iron-nickel (Fe-Ni) alloy-based invar alloy (Fe-36% Ni) is mainly used. The invar alloy produced by the conventional rolling process has difficulty in controlling the surface roughness (protrusion, pupil) and the thickness, and thus the characteristics of the device are deteriorated and the manufacturing yield is remarkably lowered. In addition, when a very thin product (18 μm or less) is produced, surface defects due to impurities and manufacturing cost increase.

The thermal expansion coefficient of the iron-nickel alloy foil manufactured through the rolling process is shown in FIG.

Accordingly, an iron-nickel alloy foil is manufactured through electroforming as a substitute for the rolling process.

In the electroplating method, an electrolytic solution is supplied through a liquid supply nozzle in a gap surrounded by a rotating cylindrical negative-electrode drum provided in an electrolytic bath and a pair of arc-shaped positive electrodes opposing to the electrolytic bath to energize a current, And then winding them to form a metal foil. The Fe-Ni-based alloy metal foil produced by the electroplating method has an advantage that the average grain size is small and the mechanical properties are excellent. In addition, the Fe-Ni alloy metal foil has a low manufacturing cost because it can be manufactured at a low manufacturing cost.

However, even when the iron-nickel alloy foil is produced by the electroplating method, the coefficient of thermal expansion greatly changes according to the crystal structure of the alloy foil, and the performance of the OLED product may be deteriorated.

Accordingly, there is a demand for the production of an iron-nickel alloy foil for an OLED having a crystal structure capable of reducing a thermal expansion coefficient in producing an iron-nickel alloy foil by the electroplating method.

Korean Patent Publication No. 2016-0077575

An aspect of the present invention is to provide an iron-nickel alloy foil capable of effectively reducing the coefficient of thermal expansion by providing a specific crystal structure in providing an iron-nickel alloy foil for an OLED, and a method of manufacturing the same.

One aspect of the present invention is an iron-nickel alloy foil produced by electroplating,

The content of nickel is 36 to 45% by weight, and the balance includes iron (Fe) and unavoidable impurities,

(111) plane, (200) plane, and (220) planes of the total sum of the texture coef fi cients of the (111) plane, the (200) The ratio of the total texture coefficient of the (200) plane is 80 to 98%, the ratio of the total texture coefficient of the (111) plane is 60 to 78%, the ratio of the total texture coefficient of the (200) plane is 20 to 30% Nickel alloy foil is 20% or less (inclusive of 0%).

According to another aspect of the present invention, there is provided a method for producing an iron-nickel alloy foil by electroplating using an electrolytic solution containing an iron compound and a nickel compound, wherein the relationship between the iron ion and the nickel ion in the electrolytic solution, ], And the f_Ni ^{2 +} value of the following formula (1) satisfies 72 to 78. The present invention also provides a method for producing an iron-nickel alloy foil,

[Equation 1]

^{f_Ni 2 + = {[Ni 2} +] / ([Ni 2 +] + [Fe 2 +])} × 100

(Where Ni ^{2 +} and Fe ^{2 +} mean the nickel ion concentration and the iron ion concentration in the electrolytic solution).

According to the present invention, it is possible to provide an iron-nickel alloy foil, which is effectively produced by controlling the crystal structure of the iron-nickel alloy foil in the iron-nickel alloy foil produced by the electroplating method, effectively reducing the coefficient of thermal expansion. There is an effect that it can be suitably applied as a material.

1 is a graph showing a thermal expansion coefficient state of an iron-nickel alloy foil manufactured by a conventional technique (rolling method).
2 is a graph showing a thermal expansion coefficient state of an iron-nickel alloy foil manufactured by the electroplating method, (iron: nickel alloy foil having an FCC structure, (Comparative example).
FIG. 3 shows X-ray diffraction analysis results of an iron-nickel alloy foil having an FCC structure according to an embodiment of the present invention.
4 shows X-ray diffraction analysis results of an iron-nickel alloy foil having an FCC + BCC structure according to an embodiment of the present invention.

The present inventors have intensively studied ways to lower the thermal expansion coefficient of the iron-nickel alloy foil in providing an iron-nickel alloy foil manufactured using electroforming. As a result, it was confirmed that the coefficient of thermal expansion of the iron-nickel alloy foil varied depending on the crystal structure of the iron-nickel alloy foil.

Accordingly, the present invention is technically advantageous in providing an iron-nickel alloy foil having a crystal structure capable of lowering the thermal expansion coefficient.

The present invention is described in detail below.

An iron-nickel (Fe-Ni) alloy foil, which is one aspect of the present invention, is manufactured by electroplating and has a content of nickel of 36 to 45% by weight and the balance of Fe and unavoidable impurities. (FCC, Face-Centered Cubic).

When the structure of the iron-nickel alloy foil is not a face-centered cubic structure (FCC), but a face-centered cubic structure (FCC) and a body-centered cubic structure (BCC) are formed simultaneously or a cubic structure (BCC) is formed, the thermal expansion coefficient is effectively lowered There is a problem that it is not suitable for use as a material for an OLED.

More specifically, the present invention relates to a method for fabricating a semiconductor device having a ratio of a sum of texture coef fi cients of a (111) face and a (200) face to a total sum of a texture coef fi cient of a (111) face, The ratio of the aggregate texture coefficient of the (200) plane is 20 to 30%, the ratio of the aggregate texture factor of the (220) plane is 20 to 98%, the ratio of the texture coefficients of the (111) Or less (including 0%).

If the numerical range of the aggregate texture coefficient is not satisfied, a large difference in thermal expansion coefficient occurs in the width direction of the iron-nickel alloy foil, which may cause a problem of dimensional difference between the substrate and the mask during the deposition process.

Here, the aggregate texture coefficient (TC) is obtained by obtaining the diffraction intensity peak value of each crystal plane by X-ray diffraction (XRD) as shown in FIG. 2 and then comparing it with the reference peak value, Within the range. To I (hkl) from the equation (2) represents the measured diffraction intensity of the face _{(hkl), I 0 (hkl} ) is ASTM (American Society of Testing Materials) standards shows a diffraction intensity of a standard powder-like diffraction data.

&Quot; (2) "

TC (hkl) ≥ {I ( hkl) / I 0 (hkl)} / [1 / nΣ {I (hkl) / I 0 (hkl)}]

It is preferable that the iron-nickel alloy foil of the present invention having the above-mentioned aggregate texture factor has a nickel content of 36 to 45 wt%.

When the nickel content is low, there is a problem that the thermal expansion coefficient sharply increases. Therefore, it is preferable that the nickel content is 36 wt% or more. However, if the content is excessively high and exceeds 45% by weight, the coefficient of thermal expansion of the alloy foil becomes too large as compared with glass or the like, and thus the material can not be suitably used as a material for OLED.

Therefore, in the present invention, it is preferable to limit the nickel content of the iron-nickel alloy foil to 36 to 45 wt%.

Except for the above-mentioned nickel content, the other component is Fe. However, in the ordinary manufacturing process, impurities which are not intended from the raw material or the surrounding environment may be inevitably incorporated, so that it can not be excluded. These impurities are not specifically mentioned in this specification, as they are known to any person skilled in the art of manufacturing.

The iron-nickel alloy foil of the present invention, which has the above-mentioned texture and whose nickel content is controlled, can achieve the target low thermal expansion coefficient by satisfying the thermal expansion coefficient of 3.0 to 5.0 ppm / K.

The iron-nickel alloy foil of the present invention satisfies the conditions (JIS standard) required for a material for OLED to have a surface roughness (Rz) of 2 탆 or less and further has a characteristic in which the weight deviation in the width and length direction is 3% or less .

If the surface roughness Rz exceeds 2 탆, the surface is uneven and there is a possibility that a difference in etching depth occurs during the etching process.

In addition, when the weight deviation of the alloy foil in the width direction and the longitudinal direction exceeds 3%, there arises a problem that physical property deviation occurs on the surface, curl increases, and the coefficient of thermal expansion becomes uneven.

Here, the weight deviation was determined by cutting the iron-nickel alloy foil to an area of 5.8 cm x 5 cm to prepare a specimen, measuring the weight of the specimen, calculating the iron-nickel alloy weight per unit area, The procedure of cutting the specimen along the width direction of the foil is repeatedly performed to calculate the weight value of the iron-nickel alloy foil for each specimen and then calculating the standard deviation.

As described above, since the structure of the iron-nickel alloy foil is formed into the face-centered cubic structure, the strength and ductility can be secured at 1.0 to 1.5 GPa and 1 to 5%, respectively, by controlling the inter-

The iron-nickel alloy foil of the present invention having the above-mentioned physical properties preferably has a thickness of 4 to 50 탆.

Meanwhile, the iron-nickel alloy foil of the present invention can be produced by electroplating. More specifically, a negative electrode and a positive electrode are provided in an electrolytic bath containing an iron compound and a nickel compound and an electric potential is applied through a current device. Whereby the Fe-Ni alloy is electrodeposited on the surface of the negative electrode.

In the present invention, the method for producing the iron-nickel alloy foil by the electroplating method is not particularly limited. For example, the iron concentration is 5 to 20 g / L, the nickel concentration is 20 to 50 g / L and 20 g / ) Of boron, boron of 5 g / L or less (excluding 0), and saccharin of 100 ppm or less (excluding 0).

Among the electrolytic solution components, boron and saccharin are added to obtain an alloy foil which is smooth and excellent in glossiness. In particular, saccharin is a polish agent for obtaining a fine thin film layer by giving gloss to the surface of an alloy foil, It is a stress relieving agent.

Here, a small amount of ascorbic acid can be added for the purpose of preventing oxidation of the electrolytic solution.

The remaining solvent of the electrolytic solution is preferably pure water, more preferably ultra pure water.

In addition, iron having a concentration of 5 to 20 g / L may be dissolved in the form of a salt such as iron sulfate, ferric chloride, or ferrous sulfate or may be supplied by dissolving iron or iron powder in hydrochloric acid or sulfuric acid. Nickel having a concentration of 20 to 50 g / L may be used in the form of salts such as nickel chloride, nickel sulfate, and nickel sulfamate, or may be prepared by dissolving ferronickel or the like in an acid.

The Fe-Ni alloy foil produced by the electroplating method may be varied not only by the concentration of Fe and Ni in the electrolytic solution but also by the kind and content of other added components, process conditions, and the like. For example, when the concentration of iron in the electrolyte is increased, the Fe component of the alloy becomes higher, and when the current density becomes lower, the Fe component becomes higher, so that it is important to control them.

Particularly, in the present invention, the concentration of iron and nickel in the electrolytic solution and the process conditions for electroplating are important means for obtaining the intended aggregate structure coefficient in the production of the iron-nickel alloy foil. Specifically, the relationship between the iron ion and the nickel ion It is preferable that the f_Ni ^{2 +} value represented by the following formula (1) satisfies 72 to 78:

[Equation 1]

^{f_Ni 2 + = {[Ni 2} +] / ([Ni 2 +] + [Fe 2 +])} × 100

(Where Ni ^{2 +} and Fe ^{2 +} mean the nickel ion concentration and the iron ion concentration in the electrolytic solution).

The production of iron-nickel alloy foil by electroplating is complicated by anomalous codeposition in which iron, which is a nonmetal metal, preferentially precipitates over nickel, which is a precious metal. Even if it is desired to obtain a desired composition, Considering the ratio of the ions, the concentration of Ni ions should be relatively larger than the concentration of Fe ions in view of the composition of electrodeposited electrodeposits.

Therefore, when the f_Ni ^{2 +} value expressed by the above-mentioned formula (1) satisfies 72 to 78, an iron-nickel alloy foil having a desired nickel content can be obtained while having a face-centered cubic structure (FCC) structure.

If the value of f_Ni ^{2 +} is less than 72 or exceeds 78, an iron-nickel alloy foil having an FCC + BCC mixed crystal structure is formed, so that the target thermal expansion coefficient can not be secured.

In the case of using the above-described controlled electrolyte for obtaining the iron-nickel alloy foil of the present invention, it is preferable to use a solution having a pH of 1.5 to 2.5, a temperature of 45 to 70 캜, a current density of 10 to 40 A / dm ² and a flow rate of 20 to 45 m ³ / As shown in Fig.

At this time, if the pH is too low, pits are formed on the surface of the iron-nickel alloy foil during the production of the iron-nickel alloy foil, which makes it difficult to continuously operate the nickel-nickel alloy foil. However, if the pH is too high, there is a problem that continuous operation is impossible due to the occurrence of electrolytic sludge, and the nickel composition is excessively increased, making it impossible to produce an iron-nickel alloy foil of a desired composition.

In consideration of this, the pH preferably satisfies 1.5 to 2.5.

If the current density is too low or too high, an FCC + BCC mixed crystal structure is formed, and the nickel composition of the alloy foil fails to meet the target level.

Therefore, it is preferable that the current density is set so that the FCC crystal structure is formed within the range of 10 to 40 A / dm ² .

Also, when the temperature is too high or the flow rate is too low, a mixed crystal structure of FCC + BCC is formed.

If the temperature is too high or the flow rate is too low, the nickel composition becomes low, while if the temperature is too low or the flow rate is excessively high, the nickel composition increases.

Therefore, it is preferable that the temperature is controlled to 45 to 70 ° C, the flow rate is controlled to 20 to 45 m ³ / hr, and the FCC crystal structure is formed within the range.

Hereinafter, the present invention will be described more specifically by way of examples. It should be noted, however, that the following examples are intended to illustrate and specify the present invention, but not to limit the scope of the present invention. And the scope of the present invention is determined by the matters described in the claims and the matters reasonably deduced therefrom.

( Example )

In an electrolytic bath containing an electrolytic solution containing an iron concentration of 5 to 20 g / L, a nickel concentration of 20 to 50 g / L, chlorine of 20 g / L or less, boron of 5 g / L or less and 100 ppm or less of saccharin, The electrolyte solution was supplied at a temperature of 45 to 70 캜, a current density of 10 to 40 A / dm ² and a flow rate of 20 to 45 m ³ / hr to prepare an iron-nickel alloy foil.

The crystal structure and thermal expansion coefficient of each of the prepared iron-nickel alloy foils were measured, and the results are shown in Table 1 below. At this time, the crystal structure was confirmed by X-ray diffraction analysis, and the texture constants were obtained as described above.

For the measurement of mechanical properties, tensile strength specimens were prepared on the basis of ASTM-SUB and measured using a micro tensile tester at a strain speed of 1 μm / sec.

The ratio (f_Ni ^{2 +} ) according to the metal ion content in the electrolyte and the nickel content of the produced iron-nickel alloy foil were measured and are shown in Table 1 below.

division decision
rescue (%) Ni content
(weight%) f_Ni ^{2 +} Seal
burglar
(GPa) Thermal expansion
Coefficient
(ppm / K) (111)
if (200)
if (111) plane +
(200) face (220)
if Inventory 1 FCC 72.2 22.8 95.0 5.0 40.3 72.2 1.34 3.98 Inventory 2 FCC 74.7 21.1 95.8 4.2 39.5 75.3 1.40 4.42 Inventory 3 FCC 74.4 21.4 95.8 4.2 40.0 74.7 1.37 4.44 Honorable 4 FCC 69.5 24.8 94.3 5.7 41.9 76.2 1.18 3.74 Inventory 5 FCC 64.6 24.9 89.5 10.5 42.6 76.6 1.08 3.73 Inventory 6 FCC 68.3 25.2 93.5 6.5 42.2 77.0 1.12 3.88 Honorable 7 FCC 69.6 24.8 94.4 5.6 41.8 76.9 1.21 3.85 Honors 8 FCC 67.5 24.6 92.1 7.9 43.1 77.9 1.15 4.19 Proposition 9 FCC 72.7 22.5 95.2 4.8 42.1 75.4 1.29 4.10 Inventory 10 FCC 71.9 23.3 95.2 4.8 41.1 74.1 1.22 3.82 Exhibit 11 FCC 68.1 23.7 91.8 8.2 39.8 72.4 1.12 3.35 Inventory 12 FCC 74.7 21.2 95.9 4.1 41.2 73.5 1.41 4.39 Comparative Example 1 FCC + BCC - - - - 40.2 71.6 1.24 5.26 Comparative Example 2 FCC + BCC - - - - 41.5 79.4 1.11 5.92 Comparative Example 3 FCC + BCC - - - - 40.7 78.5 1.15 5.82 Comparative Example 4 FCC + BCC - - - - 41.1 80.5 1.14 5.92 Comparative Example 5 FCC + BCC - - - - 41.8 81.9 1.17 5.61 Comparative Example 6 FCC + BCC - - - - 40.2 71.7 1.14 5.80 Comparative Example 7 FCC + BCC - - - - 38.5 67.6 1.05 6.28 Comparative Example 8 FCC + BCC - - - - 38.5 68.2 1.09 6.24

The iron-nickel alloy foils of Inventive Examples 1 to 12, which were manufactured satisfying all the conditions of the present invention, all have an FCC structure and can be confirmed to exhibit a low coefficient of thermal expansion.

On the other hand, in each of Comparative Examples 1 to 8 in which the value of f_Ni ^{2 +} does not satisfy the condition of the present invention, a mixed structure of FCC and BCC was formed, and therefore, the thermal expansion coefficient was high.

The thermal expansion coefficients of Examples 1 to 12 and Comparative Examples 1 to 8 are shown graphically according to the nickel content.

As shown in FIG. 2, it can be seen that the thermal expansion coefficients of the inventive examples having the FCC structure are lower than those of the comparative examples having the FCC + BCC structure.

FIG. 3 shows the results of X-ray diffraction analysis of the iron-nickel alloy foil according to the present invention, and it can be confirmed that (111), (200) and (220) peaks appear.

FIG. 4 shows the results of X-ray diffraction analysis of an iron-nickel alloy foil having an FCC-BCC structure. It can be seen that not only the peak of the FCC structure but also the peak of the BCC structure appear together.

Claims (9)

An iron-nickel alloy foil produced by electroplating,
The content of nickel is 36 to 45% by weight, and the balance includes iron (Fe) and unavoidable impurities,
(111) plane, (200) plane, and (220) planes of the total sum of the texture coef fi cients of the (111) plane, the (200) The ratio of the total texture coefficient of the (200) plane is 80 to 98%, the ratio of the total texture coefficient of the (111) plane is 60 to 78%, the ratio of the total texture coefficient of the (200) plane is 20 to 30% 220) plane is less than or equal to 20% (including 0%).
The method according to claim 1,
The iron-nickel alloy foil has a coefficient of thermal expansion (CTE) of 3.0 to 5.0 ppm / K.
The method according to claim 1,
Wherein the iron-nickel alloy foil has a surface roughness (Rz) of 2 탆 or less.
The method according to claim 1,
Wherein the iron-nickel alloy foil has a weight deviation of 3% or less in the width direction or the length direction.
The method according to claim 1,
The iron-nickel alloy foil has a tensile strength of 1.0 to 1.5 GPa and an elongation of 1 to 5%.
The method according to claim 1,
Wherein the iron-nickel alloy foil has a thickness of 4 to 50 占 퐉.
A method for producing an iron-nickel alloy foil by electroplating using an electrolytic solution containing an iron compound and a nickel compound,
Wherein the relationship between the iron ion and the nickel ion in the electrolytic solution is represented by the following formula (1), and the f_Ni ^{2 +} value in the following formula (1) satisfies 72 to 78: Way.

[Equation 1]
^{f_Ni 2 + = {[Ni 2} +] / ([Ni 2 +] + [Fe 2 +])} × 100
(Where Ni ^{2 +} and Fe ^{2 +} mean the nickel ion concentration and the iron ion concentration in the electrolytic solution).
8. The method of claim 7,
Wherein the electrolytic solution contains an iron concentration of 5 to 20 g / L, a nickel concentration of 20 to 50 g / L, a chlorine of 20 g / L or less, a boron of 5 g / L or less and a saccharin of 100 ppm or less .
8. The method of claim 7,
Which is carried out at a pH of 1.5 to 2.5, a temperature of 45 to 70 캜, a current density of 10 to 40 A / dm ² and a flow rate of 20 to 45 m ³ / hr in the production of an Fe-Ni alloy foil by the electroplating method, A method for producing an alloy foil.

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