WO2009038265A1

WO2009038265A1 - Electrochromic device with multiple pattern for camera, and manufacturing process thereof

Info

Publication number: WO2009038265A1
Application number: PCT/KR2008/001972
Authority: WO
Inventors: Seung Wook Han; Jin Ho Choi; Dong Eon Kim; Byung Gil Lim; Hyeon Jeong; Seung Min Paek; Joo Hee Kang
Original assignee: Dansuk Industrial Co., Ltd.
Priority date: 2007-09-21
Filing date: 2008-04-08
Publication date: 2009-03-26
Also published as: KR20090031045A

Abstract

The present invention relates to an electrochromic device with multiple pattern for a camera which is able to control the amount of light, which comprises a pair of conductive glass substrates (24) that transparent conductive material layer (21) with the different-sized multiple pattern are laminated on the a pair of transparent glasses (20) placed at some distance; cathodic/anodic coloration materials laminated in the same pattern as the multiple pattern of transparent conductive materials on each conductive glass substrate (24); and an electrolyte lied between each electrochromic materials, and, and to a manufacturing process thereof.

Description

ELECTROCHROMIC DEVICE WITH MULTIPLE PATTERN FOR CAMERA, AND MANUFACTURING

PROCESS THEREOF

Technical Field

[I] The present invention relates to an electrochromic device with multiple pattern for a camera which is able to control the amount of incident light on camera lens, and to a manufacturing process thereof.

Background Art

[2] The traditional diaphragm of many kinds of cameras, such as mechanical cameras, digital cameras, medical cameras, etc. is mainly the mechanical diaphragm (patent document 1), and the liquid crystal diaphragm with LCD is also known (patent document 2).

[3] Recently, the technology about liquid crystal display (LCD) as a terminal display method has been mostly applied, but there are some drawbacks that LCD is visually limited because display contrast depends on the seeing direction, and LCD is not able to memorize when power is turned off. The rising alternative device of LCD is an electrochromic device (ECD), which resolves the limit of visual angles. Furthermore, it is economic owing to its low drive- voltage, and it has a memory capacity, thereby ECD being suitable for the next generation display method.

[4] Electrochromic is that the optical density or reflectance on the particular wavelength area in the process of ion injection into the interior of materials is reversibly changed. Materials with svch characteristics are largely classified by cathodic coloration type materials such as WO , TiO , MoO , NbO , V O , etc., and anodic coloration type

3 2 3 3 2 5 materials such as KFeIn[FeH(CN) ], NiO , Cr O , MnO , Fe O , etc. The chemical

6 2 2 3 2 2 3 reaction of the well-known electrochromic transition metal oxides is as follows: [5] Reduction coloration : MO + x(I⁺ + e ) « I MO n x n

[6] (decoloration) (coloration)

[7] Oxidation coloration : I MO <→ MO + x(I⁺ + e ) x n n

[8] (coloration) (decoloration)

[9] n = 1 (rock-salt)

[10] 1.5 (carborundum)

[I I] 2 (rutile) [12] 3 (defect perovskite)

[13] I = H, Li, Na, K

[14]

[15] Such materials can have the electrochromic characteristics, further being divided by the cathodic coloration type and the anodic coloration type is caused by their fine crystalline structures and internal electronic structures. Such phenomena are due to the electronic absorption band of other visual area being shown in the process of changing into each cathodic/anodic state.

[16] The approximate constitution of ECD comprises a transparent conductive glass, the first electrochromic material (working electrode), an electrolyte, the second electrochromic material (counter electrode), and a transparent conductive glass in sequence. Herein, if it includes the second electrochromic material, it is a full cell system, but if it only includes a counter electrode material without the second electrochromic material, it is a half cell system.

[17] Up to now, in order to use ECD for various fields, the various cathodic/anodic coloration type ECDs have been developed for the various purposes. Recently, researches have been progressing to make the reaction fast by thin-filming of transition metals as well as conductive polymers, to display the various color, and to make the appropriate electrolyte.

[18] For example, the Korean Patent No.0691279 (patent document 3) disclosed a diaphragm- integrated style shutter of camera module for camera phone which comprises an internal controller for the amount of light which opens and closes the light path based on whether voltage is input or not and is placed at the optic axis which incident light through lens passes; at least one external controller for the amount of light which opens and closes the light path based on whether voltage is input or not, and is united with the center of the internal controller; an internal/external voltage input part which optionally inputs voltage to the internal/external controller for the amount of light; and consists of electronic coloring thin film with multiple layers which reversibly opaquely colors or transparently decolors by the cathodic/anodic reaction based on whether voltage is input or not by multiply laminating to apply to the front and back of the ion conductive layer and to face each counter-directional electrode layer; transparent cathode/anode layers laminating to face the front and back of the electronic coloring multiple layer-thin film by electronically connecting to the cathode/anode of the internal/external voltage input part; a protection layer laminating to face each external side of the transparent cathode/anode layer. [19] The diaphragm integrated style shutter does not require so large space to drive the device like the mechanical diaphragm device for camera in the patent document 1, the Korean Patent Laid-Open Publication No.20060045297, does. Also, it solves the problem of limitation of visual angles like an electronic shutter device using liquid display device in the patent document 2, the Korean Patent Laid-Open Publication N).1999-0008791, does.

[20] However, the composition of the diaphragm integrated style shutter for camera module in the patent document 3 has a problem of color blurring. Because the insulation constitution about the boundary between the conductor line 139 for voltage input of the internal controller 100 for the amount of light and the internal/external controller for the amount of light, the counter controller not being input voltage drives when the internal/external controller for the amount of light is voltage-input. Also, color blurring to the external controller adjacent to the conductor line 139 for voltage input occurs when the internal controller is voltage-input. Consequently, it is a problem to be difficult to precisely control the amount of light.

[21] Furthermore, when preparing the diaphragm shutter which is able to precisely control the amount of light step by step, the constituent module of the internal/external controller for the amount of light should be overlapped depending on the step of controlling the amount of light, in this case the more the module number increases, the larger the volume is. Therefore, it is limited to apply to small electronic devices (such as a cellular phone with camera function), and light transmittance in the transparent stage not being colored decreases because thickness makes transparency worsen.

[22] [Patent document]

[23] 1. Korean Patent Laid-Open Publication No.2006-0045207

[24] 2. Korean Patent Laid-Open Publication No.1999-0008791

[25] 3. Korean Patent Publication N).10-0691279

Disclosure of Invention Technical Problem

[26] Accordingly, the object of the present invention is to provide the electrochromic device (ECD) with multiple pattern to improve the quality of picture image by controlling the amount of incident light on lens of common digital cameras or cameras of cellular phone. Particularly, it is to provide the electrochromic device with multiple pattern to be able to get trust to control the amount of light by precisely controlling the amount of transmitting light, no color blurring and simply processing the coloring materials by selectively input voltage on each pattern, and the manufacturing process thereof.

Technical Solution

[27] The present inventors of the present invention conducted various researches to achieve the foregoing object. As a result, they surprisingly found that electrochromic materials with multiple pattern as a single thin film to be light transmission-controlled by masking effect, and being unified a diaphragm and a shutter by selectively inputting voltage on each pattern makes to enable ECD to apply to all kinds of cameras, in particular diaphragms of cameras of cellular phone. Thus, the present invention was accomplished. Accordingly the present invention satisfies the demand for the high resolution of camera amid the recently increasing market of the cell phonene with the camera.

[28] That is to say, the conventional camera placed in the cellular phone does not have the appropriate controlling means and masking device required for the high resolution and the high quality image, since it is so small that it is mechanically limited. Therefore, the present invention solves the said problem by using the ECD with multiple pattern.

[29] As a means to solve the technical problem, the ECD with multiple pattern for camera of the present invention is characterized by controlling the amount of transmitting light by coloring based on whether an electric current is input or not, among the devices that consist of the conductive glass substrate which transparent conductive materials of the different size with a certain pattern are laminated; the cathodic/anodic coloration materials that are film-laminated as the same pattern as the multiple pattern of the conductive glass substrate on the conductive glass substrate; the electrolyte.

[30] And, it is characterized by controlling the amount of light step by step by being composed to be independently current-input on each pattern of the multiple ECD.

[31] Herein, the multiple pattern may be a multiple concentric circle or a multiple polygon.

[32] It is characterized by preparing the conductive glass substrate using the transparent conductive ITO glass, patterning it with photolithography and wet-etching method, and forming the single thin film with cathodic/anodic coloration type materials as electrochromic material on the said conductive glass substrate.

[33] As for the cathodic/anodic materials, it is known that the compounds having functions of coloration-efficient, electrochemical durability, and complementarily electrical coloration can be utilized for this purpose, and examples thereof include tungsten oxide(WO ) and Prussian blue, KFeIH[FeII(CN) 1, which is ferrocyan iron

3 6 hydrate and can be prepared by reacting ferric chloride with ferrocyan potassium. The preparation of the electrochromic device of the present invention is characterized by positioning the former electrochromic materials on the one ITO layer, and positioning the latter electrochromic materials on the other ITO layer, thereby establishing the full cell system. Herein, in the present invention, the cathodic/anodic materials are not limited to the said compounds. [34] And the electrolyte which acts to move the ion depending on the change of the voltage is filled between the said two electrochromic material layers, and the said e lectrolyte is transparent, electrochemically-, optically-, and thermally- stable, and has the high ion-condirtivity. In the preferred embodiment of the present invention, the hydrophobic lithium ion electrolyte is illustrated, but the present invention is not limited thereto.

Advantageous Effects

[35] The present invention provides the high performance camera for cellular phone which is small and thin-film style and is able to perform the high resolution and the high quality image by unifying a diaphragm and a shutter by providing the thin-film style ECD with capability of the appropriate light controlling and masking, according to the demand for the small size of camera module for cellular phone, thin-film style, the high resolution and the high quality image.

[36] Furthermore, as the thin film coating of the different-sized multiple concentric center comprises the single thin film, even if there are a lot of patterns in the multiple pattern, such a multiple pattern can be easily manufactured by one thin-film processing and it is possible to prevent an increase of volume. And, when the voltage is independently input on each pattern, the amount of light can be precisely controlled, thereby the reliability of controlling the amount of light being improved, as the color blurring is prevented and the transparency rate is not declined.

[37] Moreover, as the increase of the volume and the depth of ECD are prevented, it can be so small that it is applied to the diaphragm shutter for the ultra thin film style camera. Brief Description of the Drawings

[38] Fig. 1 depicts a drawing of a photo mask for applying ECD of the present invention to the diaphragm for the camera.

[39] Fig. 2 depicts a drawing about condition of coating the photoresist on the conductive

ITO glass and then developing it. [40] Fig. 3 depicts a drawing about condition after wet-etching of the conductive ITO glass.

[41] Fig. 4 depicts a schematic diagram of ECD comprised by the tungsten oxide /

Prussian blue thin film and the hydrophobic electrolyte.

[42] Fig. 5 is a picture taken the depth of tungsten oxide/Prussian blue thin film by scanning electro microscopy.

[43] Fig. 6 is a graph shown the result of electrochromic characteristics and the electrochemical reaction amount of the tungsten oxide/Prussian blue thin film by cyclic voltammetry.

[44] Fig. 7 is a graph shown the result of observation of the light-transparency change about ECD comprised by the tungsten oxide/Prussian blue thin film and the hydrophobic electrolyte by ultra ray - visible ray transmission spectrum and pictures.

[45] Fig. 8 is a graph shown the result of observation of durability about ECD comprised by the tungsten oxide/Prussian blue thin film and the hydrophobic electrolyte by constant voltage/current meter and ultra rays-visible rays transmission spectrum. Best Mode for Carrying Out the Invention

[46] The present invention is explained in more details with the attached drawings

[47] Fig. 1 is a plane view of photomask used to produce ECD with multiple pattern, and

Fig. 2 is a plane view and a sectional view of the conductive ITO glass 23 which is coated by photoresist and then developed. Fig. 3 is a plane view and a sectional view of the wet-etched conductive ITO glass 24.

[48] From Fig. 2 and Fig. 3, it is understood that the designated patterning of the conductive glass 23 is proceeded through photolithography and wet-etching of the transparent conductive ITO layer 21 laminated on the transparent glass 20.

[49] In more particular, the photomask 10 with multiple pattern shown in the Fig. 1 is used to control the amount of light-transmission of the diaphragm shutter step by step by producing ECD that is able to be applied to the diaphragm shutter, but it is not intended that the pattern is limited to the shown example.

[50] The pattern of the above photomask 10 may be a multiple concentric pattern with the different-sized diameter like the figure l-(a), or a multigonal pattern with the different- sized diameter like the figure l-(b). Since this multiple pattern can make photomask 10 with other pentagonal or hexagonal patterns, we call the pattern like the figure l-(a) as the multi-concentric pattern, and the pattern like the figure l-(b) as the multigonal pattern.

[51] Herein, if the pattern gap in the multiple pattern is minimized, the number of the pattern is increased, and each pattern is independently colored, the amount of transmitting light can be precisely controlled. So, the multiple pattern of the present invention is not limited to triple pattern shown in the drawings, and it can be formed by more than triple pattern.

[52] The opaque area 11 in the photomask 10 shows the area being not transmitted by

UV, the transparent area 12 shows the area being transmitted by UV, and the lower projected area in the drawings shows a bridge area to electrode for voltage input.

[53] If the negative light-sensitive polymer (photoresist) layer 22 is formed by coating negative light-sensitive polymer onto the conductive glass 20 being laminated with the ITO layer 21 which is transparent electrode materials, and by irradiating UV ray and developing the above negative sensitive polymer with the state of placing the photomask on the top of layers, the negative light-sensitive polymer of the area not being irradiated by opaque area 11 of the photomask 10 is eliminated, as shown in Fig. 2, and therefore the negative sensitive polymer layer 22 is coated with the multiple concentric pattern, and at the same time, the rest of the negative light-sensitive polymer layer becomes a barrier to protect the ITO layer 21.

[54] Then, if the layer 21 is etched with acidic solution sirh as hydrochloric acid for 10 to

30 minutes, ITO layer 21 of the unprotected area by the negative light-sensitive polymer layer will be etched. And then, if the negative light-sensitive polymer layer is eliminated by washing, the conductive glass substrate 24 that conductive materials ITO layer 21 on the glass substrate 20 are formed can be obtained, as shown in Fig. 3.

[55] As the electrochromic materials used in the present invention, the cathodic coloration type materials and the anodic coloration type materials are included. The cathodic coloration type material includes WO , TiO , MoO , NbO , V O , and the anodic

3 2 3 3 2 5 coloration type material includes KFeIII[FeII(CN) ], MO , Cr O , NnO , Fe O . The

6 2 2 3 2 2 3 scope of the present invention shall not be limited the above cathodic/anodic coloration type materials, and those can be selected appropriately.

[56] The present invention illustrates Prussian blue as the anodic coloration material and tungsten oxide (WO ) as the cathodic coloration material for examples, but the present invention is not limited to these materials.

[57] Tungsten oxide and Prussian blue are respectively thin-filmed on the ITO glass patterned by the electrodeposition method, etc. The electrodeposition means that the method that paint particles are electrically deposited onto the working electrode when the direct current or the direct voltage flows between the working electrode and the counter electrode in the electrodeposition paint solution. This method has advantages that the film is uniformly formed on all the area of substrate and the depth or characteristics of the film can be easily controlled by adjusting the voltage, the current or time of electrodeposition.

[58] Tungsten oxide and Prussian blue that dissociation/release reaction of ions is easily attained by adjusting the fine structure exhibit deep blue when coloration, and transparency when decoloration. Compared with an organic polymer thin film which is not durable to the lithium electrolyte or noble metal that can not show the perfect transparent appearance under the cathodic condition, tungsten oxide and Prussian blue are excellent electrochromic materials for the diaphragm shutter of camera in the durability or contrast.

[59] And, if these two materials are together used as the anodic or the cathodic coloration materials in the single device, its electrochromic reaction is so complementary that coloration response function is strengthened, and the function is expanded to the broader area of the visible spectrum, thereby the materials being able to act as a photo- sensitizer.

[60] For example, the ECD of the present invention can be composed as like Fig, 4. Fig. 4 is a schematic diagram of the ECD comprised of tungsten 30 and Prussian blue 40 thin layers, and the hydrophobic electrolyte. The process for preparing the ECD of the present invention includes the step of attaching the electrode to the conducting wire patterned by the cathodic coloration material and the anodic coloration material in order to input current, the step of attaching a spacer between the electrodes, the step of filling the hydrophobic lithium electrolyte between the electrodes, and sealing the device with a sealer.

[61] In more particular, as shown in Fig. 4, it comprises the step for thin-filming tungsten oxide 30 and Prussian blue 40 as a single layer on a couple of conductive glass substrates 24 which face each other through the spacer and is separately placed at some distance, and the step for filling electrolyte between tungsten oxide layer 30 and Prussian blue layer 40. The undescribed number 25 in the drawings refers to electrodes that respectively input current into the patterned ITO conductive glass substrate 24, the number 70 refers to a sealer.

[62] Herein, the depth of the cathodic coloration type material laminated on the first conductive glass substrate 24 may be, for example, 100 to 1000 nm, the depth of the anodic coloration type material laminated on the second conductive glass substrate 24 may be 50 to 500 nm, but it can be changeable to the broader or smaller range.

[63] The electrode 50 applied to the ECD 100 of the present invention is not limited, but preferably it can be the hydrophobic lithium electrolyte that is disclosed on the Korean Patent No. 10-0224376, and that is transparent, and has a high voltage window up to 4 V, thermal stability up to 400⁰C, stability against water, and high ion conductivity. Mode for the Invention

[64] EXAMPLE 1 : MANUFACTURING OF PATTERNED ITO CONDUCTIVE

GLASS

[65] A. Pattern design

[66] Photomask 10 with triple concentric pattern described as in Fig. l-(a) was prepared in order to apply ECD to the diaphragm for the camera of cellular phone.

[67] B. Photolithography and Wet-etching

[68] The patterned ITO conductive glass was prepared by the following method.

[69] The conductive glass 23 that ITO layer 21 was laminated on the transparent glass 20 was washed with 0.5M KOH and distilled water, and then was dried under nitrogen atmosphere.

[70] After coating the ITO layer 21 of the conductive glass 23 with the negative photoresist SU- 8 2007 to be 5 to 15/M height, the photomask 10 of the example l-(a) was laid down onto it and irradiated by UV light.

[71] After the resulted one was heat-treated at 65⁰C and 9O⁰C for respectively 5 minutes, photoresist area was eliminated using SU-8 2007 developing solution, and the resulted one was washed with isopropyl alcohol, thereby the conductive glass 23 coated with the sensitive polymer having a triple concentric pattern being obtained, as shown in Fig. 2.

[72] Subsequently, ITO 21 that was not patterned by photoresist was etched by treating with 9M or more of hydrochloric acid solution for 20 minutes, thereby finally the ITO conductive glass substrate 24 that ITO layer 21 was triple concentric circle-patterned on the transparent glass 20 being prepared.

[73]

[74] EXAMPLE 2: THIN-FILMING OF ELECTROCHROMK MATERIALS

[75] The following electrochromic materials were thin-film-treating on the patterned ITO conductive glass substrates 20 of the example 1.

[76] A. Preparation of tungsten oxide thin film

[77] The electrodeposition paint solution for tungsten oxide layer 30 selected as the electrochromic material was prepared to be pH 1.5 or less by adding HCLO into the

4 mixed solution of 25mM Na WO and 12.5mM H O .

3 2 2

[78] The electrodeposition was conducted, using the constant voltage at -0.5V for 5 to 15 minutes.

[79] B. Preparation of Prussian blue thin film

[80] The electrodeposition paint solution of Prussian blue layer 40 as the electrochromic material was prepared by mixing 1OmM K Fe(CN) , 1OmM FeCl and 1OmM HCl. The

3 6 3 ₂ electrodeposition was conducted, using the constant voltage method at -lOβklcm for 3 to 15 minutes.

[81] *Standard electrode: SCE (saturated calomel electrode)

[82] *Counter electrode: FTO glass (Fluorine doped tin oxide, FTO glass)

[83] *mM: millimole

[84] *μA: microampere

[85]

[86] EXAMPLE 3: PREPARATION OF ELECROCHROMK DEVKE

[87] In order to apply thin films prepared in the example 2 to the diaphragm shutter for camera of cellular phone, the ECD 100 with the same composition as Fig. 4 was prepared, and the manufacturing method thereof is as follows:

[88] In order to improve conductivity of the electrochromic materials of the tungsten oxide layer 30 and Prussian blue layer 40, cupper tape attached in the surface of conducting wire of each thin film pattern was used as the electrode 25, a double-stick tape from 3M corporation, U.S. as the spacer 60 was fixed on the four surfaces of tungsten oxide layer 30, 350 id of the electrolyte(the permissible range is 200 to 500 id) was fallen into the spacer 60 inside, and then Prussian blue layer 40 was covered, and the device was subjected to seal with silicon adhesive to obtain the full cell system.

[89] The prepared device showed the dark blue when coloration and transparent when decoloration by +1.6V, and was able to control the amount of the transmitting light by independently inputting voltage to the conducting wire of each concentric pattern.

[90]

[91] [EXPERIMENT]

[92] EXPERIMENT 1 : SCANNING ELECTRON MKROSCOPE (SEM)

[93] Each depth and surface of tungsten oxide layer 30 and Prussian blue layer 40 laminated on the ITO layer 21 prepared by the example 1 and 2 was observed by SEM. The sample was fixed to the holder under the condition of standing each film in cross- section, and Hitachi S-4300 was used as a measuring instrument. The result is described in Fig. 5.

[94] Fig. 5(a) is the result of the patterned tungsten oxide (WO ) film; and Fig. 5(b) is the result of the patterned Prussian blue (PB) film. [95] According to Fig. 5, the depth of the ITO layer 21 is about 200 nm, the depth of the electrolyte-laminated tungsten oxide film is about 400 nm, and the depth of the electrolyte-laminated Prussian blue film is about 190 nm. The surface of the electrolyte-laminated thin-film is quite uniformed. [96] Also, the ITO layer 21 area which was not protected from photoresist 22 was clearly etched by 9M hydrochloric acid or more. [97] EXPERIMENT 2: EXAMINATION OF ELECTROCHROME CHARAC-

TERBTES AND ELECTROCHEMICAL REACTION AMOUNT THROUGH

CYCLC VOLTAMMOGRAM (CV) [98] Electrochromic characteristics and electrochemical reaction amount of each film prepared in the example 1 and 2 were examined by cyclic voltammogram (cv),

WonATech WPGlOO. The result is shown in Fig. 6 [99] Fig. 6(a) is the result of the patterned tungsten oxide (WO ) film; and the figure 6(b) is the result of the patterned Prussian blue (PB) film. [100] Each pattern film was moved in the 20 cycles in the hydrophobic electrolyte. From the result, the more the cycle was, the more uniformed the curved line was. This means that the cathodic/anodic reaction reversibly occurred. And, as the cathodic/anodic reaction of two films oxurs at the similar voltage area, it is understood that the cathodic/anodic reaction complementally oxurs at the two films. [101] To check whether dissociation/release of the electron and lithium ion oxurs reversibly or not, the ratio (Q) of charge capacity when the oxidation/reduction reaction oxurred at the 10th cycle in each pattern film was calculated. As a result, tungsten oxide film was 0.901C, Prussian blue film was 0.940C, and the ratio (Q) of each charge capacity was about 1. [102] The fact that the ratio of the charge capacity was close to 1 means dissociation/ release of the electron and lithium ion oxurred reversibly. It means that each film was stable during the oxidation/reduction reaction. It shows the device can keep being stable after many cycles. [103] [104] EXPERIMENT 3: EXAMINATION OF CHANGE OF UGHT TRANSMITTANCE

THROUGH UV-VBBLE RAY TRANSMBSION SPECTRUM AND PETURE

ANALYSE [105] The change of light transmittance (%T) of ECDs prepared from the example 1, 2 and

3 was examined by UV-visible ray transmission spectra and pictures. Perkin-Elmer lambda 35 was used as a meter. The result is shown in Fig. 7.

[106] The light transmittance was measured while current was input on the each concentric circle at +1.6V for a second.

[107] Fig. 7 (a) is the state that all multiple concentric circles are colorized.

[108] Fig. 7(b) is the state that the center concentric pattern is decolorized and the rest of the concentric patterns are colorized.

[109] Fig. 7(c) is the state that the outermost concentric pattern is only colorized.

[110] Fig. 7(d) is the state that all concentric patterns are decolorized.

[I l l] From the result of the examination of light transmittance in the wavelength of 600 nm of each graph, the light transmittance of Fig. 7 (a), (b), (c) and (d) was respectively 28%, 51%, 75% and 95%. The transmittance was controlled step by step, the difference between (a) and (b) was about 70%. Herein, since the wavelength of 600 nm is the blue area of visible ray and the prepared ECD is dark blue when it is colorized, the light irradiates at this area.

[112] If an electric current is input after increasing more than 3 patterns by minimizing the gap between patterns of photoresist 10 in Fig. 1 and narrowing the gap under the condition of insulation, the pattern is colorized or decolorized step by step. Therefore, it is possible to prepare cameras with high resolution and without color blurring by using the diaphragm shutter that is able to control the amount of light precisely.

[113]

[114] EXPERIMENT 4: EXAMINATION OF DURABIUTY BY CONSTANT VOLTAGE/CURRENT METER AND ULTRA VIOLET-VBBILE RAY TRANSMBSION SPECTRUM ANALYSE

[115] The durability of ECDs prepared in the example 1, 2 and 3 was examined through potentiostat and UV- visible ray transmission spectrum, wherein, WonATech WPGlOO and Perkin-Elmer lambda 35 were used as measuring instruments. The result is shown in Fig. 8.

[116] It is measured while switching the condition of Fig. 7 (a) and (d), the switching condition is one cycle (coloration-decoloration-coloration) at constant current (j=52.4, βk) for 100 seconds, and light transmittance was observed for 5000 cycles by this method.

[117] Delta transmittance difference (Δ%T) of the prepared ECDs was lowered from about 70% to about 60% after 5000 cycles. Generally, the durability of ECD is recognized as stable until Δ%T is lowered to 50% or less. Therefore, ECD of the present invention is electrochemically stable. [118] The above description is based on the attached drawings and the limited examples, but it is not intended to limit to those. Any person having a skill in the art may change and modify variously the present invention without special technology based on the above description, and such changes and modifications shall be considered as the scope of the claims of the present invention. Industrial Applicability

[119] The present invention provides the high performance camera for cellular phone which is small and thin-film style and is able to perform the high resolution and the high quality image by unifying a diaphragm and a shutter from providing the thin-film style ECD with capability of the appropriate light controlling and masking, according to the trendy demand for the small size of camera module for cellular phone, thin-film style, the high resolution and the high quality image.

Claims

[1] An electrochromic device for camera with multiple pattern which comprises a pair of conductive glass substrates 24 that transparent conductive materials 21 with the different-sized multiple pattern are laminated on the a pair of transparent glasses 20 placed at some distance; cathodic/anodic coloration materials laminated in the same pattern as the multiple pattern of transparent conductive materials on each conductive glass substrate 24; and an electrolyte filled between each electrochromic material layer, and is characterized in controlling the amount of light transmittance by coloration caused by voltage-input to each electrochromic material.

[2] An electrochromic device aαjording to claim 1, wherein the amount of light transmittance is controlled step by step by the way that voltage is independently input to each pattern among multiple patterns of each electrochromic material.

[3] An electrochromic device aαjording to claim 1, wherein the multiple pattern is multiple concentric or multiple polygonal.

[4] An electrochromic device aαjording to claim 1, wherein the cathodic coloration material is one selected from the group consisted of WO , TiO , MnO , NbO

3 2 3 3 and V O .

2 5

[5] An electrochromic device aαjording to claim 1, wherein the anodic coloration material is one selected from the group consisted of KFeIH[FeII(CN) 1, NtO , Cr

6 2 2

O , NnO and Fe O

3 2 2 3

[6] An electrochromic device aαjording to claim 1, wherein the electrolyte is a hydrophobic lithium ion electrolyte.

[7] An electrochromic device aαjording to any one of claim 1 to 6, wherein the electrochromic device is applied to a diaphragm shutter for camera of cellular phone.

[8] A method of manufacturing electrochromic device with multiple pattern for camera cited in claim 1, wherein it comprises the step of photolithography, using UV and laying photomask of a certain pattern after applying negative photoresist; and the step of wet-etching glass, using hydrochloric acid solution.

[9] A method aαjording to claim 8, wherein the photolithography controls the amount of light step by step based on each pattern coloration by forming multiple pattern using photomask of the different-sized multiple pattern and independently linking electrodes with each pattern. [10] A method aEording to claim 8, wherein the multiple pattern is multiple concentric or multiple polygonal. [11] A method of manufacturing electrochromic device with multiple pattern for camera cited in claim 1, wherein it comprises the step of attaching an electrode for voltage-input to each pattern that each cathodic coloration type material film and anodic coloration type material film are multiple patterned on a pair of conductive glass substrates; the step of attaching a spacer between two electrodes; the step of filling a hydrophobic lithium electrolyte between two electrodes; and the step of sealing the device with a sealer. [12] A method aαjording to claim 11, wherein the cathodic coloration type material and the anodic coloration type material are thin-filmed by electrodeposition. [13] A method aαjording to claim 11, wherein the depth of the cathodic coloration type material laminated on the conductive glass substrate is 100 to 1000 nm. [14] A method aαjording to claim 11, wherein the depth of the anodic coloration type material laminated on the conductive glass substrate is 50 to 500 nm.