JPS59181A - Fully solid electric coloring display element - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrochromic display device that utilizes the electrochromic phenomenon, and more particularly, to a dot matrix type all-solid-state electrochromic display device that has a solid electrolyte layer, is thin, and has low crosstalk. Regarding.

[Technical background of the invention]

Electrochromic display elements include segment type display elements and dot matrix type display elements.

Among these, the superior element has clear color display and good contrast, operates at low voltage, has high-speed response, and has easy control of coloring characteristics, so it is used more frequently than the former element. has been done.

As a dot matrix type display element that utilizes the electrochromy phenomenon, a solid-liquid type electrochromic display element having the structure shown in FIG. 1, for example, has been known.

In the figure, 1 is a substrate made of glass or the like, 2 row electrodes are formed in stripes on the substrate 1, 3 is an electrochromic layer made of a transition metal oxide such as tungsten oxide, 4ii is an interlayer insulating layer,
5 is a liquid electrolyte layer for supplying electrolyte to the coloring layer 3; 6 is a column electrode formed on the substrate 1' in a direction perpendicular to the row electrode 2; and 7 is a spacer.

In such a solid-liquid electrochromic display element, when a predetermined voltage (usually 1 to 5 V) is applied between the electrodes, cations are supplied from the electrolyte layer to the adjacent coloring layer, and the coloring layer It receives the cations and develops color.

[Highlights of the Background Art] 12 However, in the solid-liquid electrochromic display element described above, a clear coloring/decoloring threshold voltage is not recognized in its coloring/decoloring characteristics, and the structure of the f-son is Since a certain degree of crosstalk cannot be avoided at 1° from the angle of 1°, it has a serious drawback that it is not suitable for matrix driving. Furthermore, there was also the risk of causing an inconvenient situation such as leakage of liquid M%. The disadvantages of the former will be explained in detail below.

In order to fully exhibit the characteristics of the dot matrix type display element mentioned above, the gap between the electrodes is generally sufficiently small compared to the dot pitch (1-7< is 1/1
0 or less K) must be done. If this condition is violated, the current will not concentrate at the intersection of the row electrode and column electrode corresponding to the selected point on the IJ box, and the current will flow into the adjacent dot. This results in an inconvenient situation in which the color of the dye also develops and disappears.

For example, if we assume that the size of a normal character is 5 x 5, and we decide to express this character with 5 x 7 dots, the dot pitch should be 0.7 dots in order to avoid the above-mentioned inconvenience. Therefore, it is preferable that the gap between the electrodes is at least 1/10 of the dot pitch -F1, that is, 0.07 wm or more. However, in solid-liquid electrochromic display elements, since it is necessary to seal a liquid electrolyte between the electrodes, a gap between the electrodes of 0.5 to 1+a is usually required, and it is not possible to narrow the gap below this. . The reason is,
A dot matrix type display is used as a single character, but is rarely used, and is usually used as a character string or character matrix. This is because there is a technical restriction that requires substrates such as the above to be faced with a narrow gap of -. Therefore, there has been a demand in the art for the development of a dot matrix type element that is not subject to such technical limitations.
It is an object of the present invention to provide an electrochromic display element that exhibits a clear coloring/decoloring threshold voltage, has low crosstalk, and is thus suitable for matrix driving.

[Summary of the invention]

The main feature of the device of the present invention is that the electrolyte layer is solid.

That is, the present invention provides a stone-shaped single pole formed in a striped manner on a substrate; one or more electrochromic layers formed on a portion corresponding to the dots on the surface of the electrode; and at least one electrochromic layer formed on the upper surface of the coloring layer. one or more electrolyte layers; the electrolyte and coloring layer are sandwiched between the stone-shaped frame and formed in a direction perpendicular or oblique to the electrodes; 1. a striped column electrode; and in which at least one of the column, electrode, or row electrode is translucent;
The electrolyte layer is characterized by having a height of 10 μm or less and being solid.

The device of the present invention will be explained based on an example shown in FIGS. 2 and 3. FIG. 3 is a longitudinal sectional view of the element shown in FIG. 2.

In the figure, 1 is a substrate made of glass or the like, and 2 is a row electrode formed in a striped manner on the upper surface of the substrate 1. The row electrodes 2 are formed, for example, by vapor depositing a light-transmitting conductive material on a substrate 1 and forming the obtained film into a striped pattern. The material of the electrode 2 is I"20, +SnOtr or a mixture thereof, InyOs, 5notKC
A commonly used material such as one containing dO or the like may be used.

Reference numeral 3 denotes an electrochromic layer formed at a portion of the row electrode 2 corresponding to a dot. As the color forming substance constituting the layer 3, for example, V
20 s + WO2+ Cu20 HN 10 +
S”O+P bO+ Cet Os + T 10 +
G a20 + Agt O+ Hgt Or Tb
t0srSiO, TaO, F'eO, OsO+Aut
O+Mo0a+CrO.

CdtO! I r2o! l + MnO, UOt +
Coo! WON r U2O5+GaO, MnO
*, 5nOt+ IrtOt, NbtOs+UO3+T
e0t + CdO + CrtOs + Mn0t
, 'I'JLt05 + C0tOs,
Beafu 1AIly's + SbtOg, Ti1
t + Cent + Sbt Us + Ago +
FevOs is opened, and three electrochromic layers are formed of one or a mixture of two or more selected from these. Note that the layer 3 may be two or more layers.

Reference numeral 4 denotes an interlayer insulating layer formed of a stow or the like formed on the upper surface of the row electrode 2 other than the portion corresponding to the dots. still,
In principle, it is possible to form an element even if the layer 4 is not formed, so in the element of the present invention, no particular disadvantage occurs even if the layer 4 is not formed.

5' is a solid electrolyte layer formed on the soil surface of the coloring layer 3 and the insulating layer 4. The materials constituting the layer 5' include:
For example, S 10 + Sl 02 + 1rOt +
YtOs +Yt)tOs + 5et03 + c
r2o31 N jO+ VtO* + IV[n02
1Ta2051 Ge0t + GdtOs r Tl
Metal oxides such as O2 - MgF2 + CF'F2 r
LfF HLI I, pbp', , B IF
Halides such as 2; other L ] s N + Si
NTANON and Ni (Off)z are examples. The above-mentioned substance CJ1 No. 1. This is also different from the liquid electrolyte of solid-liquid devices.

The solid electrolyte layer 5' is made of one kind or a mixture of two or more kinds selected from the above-mentioned materials. In addition, the layer 5' is 2
There may be more than one layer, or as shown in FIG. 4, only the coloring layer 30 may be formed in a single layer. In the latter case, crosstalk is further reduced, which makes it even more preferable.

Reference numeral 6 designates column electrodes formed in stripes in a direction perpendicular to the row electrodes 2 on the upper surface of the electrolyte layer 5'.

As the electrode 60 phase a, 4+ and 4 of the row electrode 2 described above are used.
Examples are similar to self. At least one of the poles is translucent. Incidentally, the column electrode 6 may be formed in the direction diagonally opposite to the row N and the pole 2, if necessary.

In the device of the present invention having the above-described structure, crosstalk is not sufficiently reduced when the coloring layer 3, ηa, and desolate layer 5' are combined and tV exceeds 10 μm or more. The device of the present invention shows a clear threshold voltage L2
, and the crosstalk is made small. W) VC is
The combination of coloring substance and solid electrolyte, for example, WOs
and MgFt, WON and zro.

WO3 and Cr, Os, WOs and Vt Os, WO
s and Zr0t (addition of 5-20 wt% Y t Os)
, WON and ZrO (adding 5 to 20% Y and Os)/vtos is preferably a two-layer laminated electrolyte.

However, even if the coloring/decoloring voltage is not clear, it is sufficient to perform matrix driving that does not short-circuit a selected point in the coloring state.
, the combination is not limited to the above. As a matrix driving method that does not cause short-circuiting of selected points, 1) For example, as shown in FIG. An example of this is a driving method in which the electrodes in column 1 are left open.

In the device of the present invention, for example, a transparent conductive material is vapor-deposited on a substrate, this is battened into stripes to form a thin film-like row electrode, and then insulation is applied on the row electrode if necessary. A material, a coloring material, and a solid% WF material are sequentially deposited, and then the material is deposited on a light-transmitting or non-light-transmitting conductor 1, and then this is formed into stripes (tanned to form a column electrode). easily manufactured by J
l,ru.

In the device of the present invention manufactured in this manner, the eyes, coloring layer, and electrolyte layer can be formed by vapor deposition, etc., so the combined thickness of these layers is 10 μm or less, and as a result,
The gap between the electrodes also becomes narrower. In this regard, when compared with the case of solid-liquid elements, the ratio of dot pitch to electrode gap is approximately 1 degree! 71. In the case of solid-liquid elements, the limit is 1 = 2, and it is difficult to exceed this limit from the point of view of mechanical strength (due to technology-7 restrictions), whereas the present invention For all-solid-state devices, the ratio is 1:1.000.
reach up to. Therefore, the device of the present invention has much smaller crosstalk than a solid-liquid type device.

[Embodiments of the invention]

Examples: WOs as an electrochromic substance, Zr as a solid solute.
The device shown in FIG. 2 was manufactured by the method shown below using a mixed oxide in which 02, 10-year grade Y, and 03 were added.

A mixed oxide with J3 (hereinafter abbreviated as ITO) containing 5 mol % of S'nOt was deposited on the glass substrate 1 to form a transparent electrode. The sheet resistance of the electrode was 30Ω0. The electrode was then etched with IlI O, 5wn big-07, length 100 mm by photolithography.
The electrodes 2 were formed in a striped pattern by applying 40 electric currents (1). Next, only the portions corresponding to the dots of the row electrodes 2 were covered with photoresist using a built-in mask. ψ
It is formed on a SiO2 film with a thickness of approximately 0.3 μ·n by sputtering, and then the l/cyst is immersed in a stripping solution to remove the part corresponding to the dot/row electrode 2. An interlayer insulating layer 4 made of sio was formed on the substrate 1. Subsequently, after forming a WO3 film with a thickness of about 0.3 μm by vapor deposition, an electrochromic layer 3 made of WO3 was formed only on the portions corresponding to the dots of the row electrodes 2 by photolithography. 3 and on the insulating layer 4. 7. r 02 and Yz
A solid electrolyte layer 5' having a thickness of approximately 0.3 mm was formed by vapor-depositing a mixed oxide with 0.03 mm. Next, a photoresist is applied to the electrolyte layer 5' and exposed to light using a mask, thereby forming a pattern with a pitch of 0.5 wn in the direction orthogonal to the row electrode 2.
A resist pattern with an M length of 60 rrrm was formed. At the very top, a transparent electrode consisting of the pattern 1-1 is vapor-deposited using a lift-off process to form a row of poles 6. /(ZrOt
+YtOs)/ITO type device was manufactured.

When we investigated the color density and applied voltage of this element, we found that it had a clear threshold voltage (2e 2 V) as shown in Figure 5.
was recognized. The response time for a change in absorbance (ΔOD) of about 0.05 seconds when applying ±3.0 cm was 0.3 seconds.

Since the threshold voltage was clear in this way, the device was then tested at 0. Matrix driving as shown in FIG. 6 was performed using three states of ±l 5 V. Pulse I+] 0.
When the rectangular wave shown in 1 was applied for 3 seconds, ΔOD
is ()5 at selected point A, 0 at non-selected point 1), half-selected point B,
005 in C, and the crosstalk was extremely low.The storage time of the display was about 0.05 hours.

Next, matrix driving as shown in FIG. 7 was performed. In this driving method, the rows related to the selection point '(dark, dark,
Since the electrodes other than the pole and column electrodes were in the open state, and the row electrodes and column g camellias related to the selected points after pressure application were set to open state 17, the selected points in the colored state would not be short-circuited, and the selected points in the colored state would not be short-circuited. As a result, storage time becomes longer. With this driving method, tJ, 6
V, 3V.

Four states were used: 0V and open. Applying a rectangular wave (corresponding to switch opening/closing operation) for 03 seconds during the pulse]7, Δ
01) was 0.5 and 0.0 at the selected point A, the non-selected point l), and the semi-selected points B and C, respectively.

At this time, the display storage time was about 3 hours.

Comparative Example A solid-liquid type device shown in FIG. 1 was manufactured using a propylene carbonate solution (1 mol/) of lithium perchlorate (LiC) 04) as a liquid electrolyte. Row electrode 2 and column electrode 6
The dimensions of are the same as in the previous embodiment. The gap between the electrodes is 0.5
I was panting.

The device did not exhibit a clear color development/decolorization threshold voltage.

Therefore, the crosstalk to the half-selected points becomes large, making it impossible to perform the matrix drive shown in FIG. 6.

Next, when the element was driven in the same manner as described above in the method shown in FIG. 7, ΔOD was at the selected point A and the half-selected point B.

The C2 non-selection points were 0.2, 0.1, and 0, respectively. Moreover, even at the half-selected points E and F, which are far from the selected point, ΔOD was 005, which was extremely thick, and loss talk was observed.

From the results shown below, the all-solid-state device of the present invention has a clear VA.
It was found that the crosstalk was small and showed the N river.

〔Effect of the invention〕

Since the device of the present invention exhibits a clear threshold voltage for developing and fading color and has small crosstalk, the color display is clearer than that of the solid-liquid type device, and the contrast is still good. Moreover,
It operates at low voltage and has high-speed response.1 It also has the advantages unique to dot matrix type elements, such as easy control of color development characteristics, and is also extremely thin. The device is most suitable as a dot matrix type device.

[Brief explanation of drawings]

FIG. 1 is a longitudinal sectional view showing an example of a striped solid-liquid electrochromic display element, FIG. 2 is a perspective view showing an example of an all-solid-state electrochromic display element of the present invention, and FIG. FIG. 4 is a vertical cross-sectional view showing another example of the device of the present invention, and FIG.
．． )) and the applied voltage, the relationship curve for the 6th country is 0. ±1■
Fig. 7 is a diagram showing a mode of IJ drive using the three states (3), and Fig. 7 shows a mode of illumination matrix drive using four states of 6V, 3V, OV, and open. 1.1'... Substrate 2... March, pole 3... Electrochromic layer 4... Interlayer insulating layer 5... Liquid electrolyte layer 5'... Solid electrolyte 11 layers 6... column electrode
7... Sveza Figure 2 Figure 3 Figure 4 Figure 61A 1.5V Figure 7 51

Claims (3)

[Claims] (1) Row electrodes formed in a striped pattern on the substrate; one or more electrochromic layers formed on the upper surface of the electrodes corresponding to dots; and at least one or more electrochromic layers formed on the upper surface of the coloring layer. consisting of an electrolyte layer; a striped column electrode sandwiching the electrolyte and the coloring layer between the row electrode and formed in a direction perpendicular or oblique to the electrode; In an electrochromic display element, at least one of which is translucent, the combined thickness of the coloring layer and the electrolyte layer is 1977 m.
An all-solid-state electrochromic display device having the following properties and characterized in that the electrolyte layer is solid. (2) The all-solid-state electrochromic display element according to claim 1, wherein the electrolyte layer is a solid electrolyte layer made of a substance exhibiting a coloring/fading threshold voltage. (3) The electrolyte layer is made of SiO, 810, ZrO,
Y.O. YbtOs + G dt03 + S e20s,
Cr20s + N to, ■2041 *Gem
, I TatOs , Tjot rMnOt, MgFt
, caFt +LiF, LiI +PbFt+B'F
t, L1. N+ SiN, A/, N. 1'H (011), 1-< is 2
The all-solid-state electrochromic display element according to claim 1, which is a solid electrolyte layer comprising more than one substance.