# Patent

## Title
Method and apparatus for providing color changing thin film material

## Abstract

An electrochromic device and methods for forming the same are provided. The device includes first and second electrodes. A layer of (GexSe100-x)100-yMny is between the first and second electrodes.

## Background
FIELD OF THE INVENTION
The invention relates to a chromogenic device and particularly to a chalcogenide-based electrochromic device.
BACKGROUND
Optical wavelengths are typically referred to as radiation encompassing UV, visible and infra-red wavelengths of about 200 nm to 25,000 nm. Solar radiation on earth's surface is generally between 290 nm and 2500 nm. Chromogenic devices that change optical properties include liquid crystal devices, suspended particle devices, user controllable photochromic devices and electrochromic (EC) devices. Electrochromic devices include an electrochromic material that, for example, changes color in response to an applied voltage. Such devices have numerous applications, including displays, vehicle window and mirror applications, among others.
The invention provides a novel type of electrochromic device.
SUMMARY
Embodiments of the invention provide an electrochromic device and methods for forming the same are provided. The device includes first and second electrodes. A layer of (GexSe100-x)100-yMny is provided between the first and second electrodes.
The foregoing and other features of the invention will become more apparent from the detailed description of exemplary embodiments provided below with reference to the accompanying drawings.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross sectional view of a device according to an exemplary embodiment of the invention;
FIG. 2 is a graph depicting a possible explanation for the operation of the device of FIG. 1;
FIGS. 3A-3C illustrate the device of FIG. 1 at various processing stages; and
FIG. 4 is a block diagram of a system including a memory device according to an exemplary embodiment of the invention.



DETAILED DESCRIPTION OF THE INVENTION
In the following detailed description, reference is made to various specific embodiments of the invention. These embodiments are described with sufficient detail to enable those skilled in the art to practice the invention. It is to be understood that other embodiments may be employed, and that various structural, logical and electrical changes may be made without departing from the spirit or scope of the invention.
The term “substrate” used in the following description may include any supporting structure including, but not limited to, a semiconductor substrate that has an exposed substrate surface. A semiconductor substrate should be understood to include silicon, silicon-on-insulator (SOI), silicon-on-sapphire (SOS), doped and undoped semiconductors, epitaxial layers of silicon supported by a base semiconductor foundation, and other semiconductor structures. When reference is made to a semiconductor substrate or wafer in the following description, previous process steps may have been utilized to form regions or junctions in or over the base semiconductor or foundation. The substrate need not be semiconductor-based, but may be any support structure suitable for supporting an integrated circuit, including, but not limited to, metals, alloys, glasses, polymers, ceramics, and any other supportive materials, as is known in the art.
The invention is now explained with reference to the figures, which illustrate exemplary embodiments, and throughout which, like reference numbers are used to indicate like features. FIG. 1 depicts an exemplary embodiment of an electrochromic device 100 constructed in accordance with the invention. The device 100 is shown as a single device 100 for simplicity, but in practice the device 100 can be one of an array of like devices.
The device 100 is supported by the substrate 10. Over the substrate is an insulating layer 11. A first electrode 21 overlies the insulating layer 11 and substrate 10. The first electrode may be any suitable conductive material and is preferably tungsten.
A layer of electrochromic material, specifically, a layer 30 of germanium-selenide-manganese glass is provided over the first electrode 11. The layer 30 can be about 450 Angstroms (Å) thick. According to the invention, the germanium-selenide-manganese glass has a stoichiometry of (GexSe100-x)100-yMny. Preferably x is less than or equal to about 30 and y is less than or equal to about 10. In one embodiment, the germanium-selenide-manganese has a stoichiometry of about Ge20.2Se70.8Mn9.0.
Electron paramagnetic spectroscopy was performed on the Ge20.2Se70.8Mn9.0 glass to determine the oxidation state and binding environment of the Mn2+ in the glass. It was shown that both Mn2+ and Mn3+ existed in the glass network. Mn2+ and Mn3+ denote the respective oxidation states of the manganese. The Mn2+ environment was unusual and exhibited a g 4.1 resonance as opposed to the usual g 2 resonance.
A second electrode 22 is over the layer 30. The second electrode preferably comprises silver and is preferably about 200 Å thick.
The first and second electrodes 21, 22 are connected respectively to voltage source 25, whereby a voltage can be applied to the device 100. In response to the application of the voltage, the color of the layer 30 changes. Using a germanium-selenide-manganese layer 30 having a stoichiometry of about Ge20.2Se70.8Mn9.0 the device 100 exhibits a continuous color change from blue to a yellow color in the 0V to 6V range when observed under white light illumination.
Without being limiting, FIG. 2 illustrates a possible explanation for the color change in response to the applied electric field. It is believed that the color change is caused by the change in energy level separation by the application of an electric field, or the Stark effect. FIG. 2 is a graph of the electric field versus energy. At 0V, the energy separation depicted by energy difference 222 and the observed color is, for example, blue because the absorbed light energy has an energy equal to the energy difference 222. When the electric field is increased to 6V, the energy separation is larger, depicted by separation 224. Thus, the absorbed light is higher energy and the observed color is, for example, yellow.
FIGS. 3A and 3B illustrate a method of forming a device 100 according to an exemplary embodiment of the invention. No particular order is required for any of the actions described herein, except for those logically requiring the results of prior actions. Accordingly, while the actions below are described as being performed in a specific order, the order is exemplary only and can be altered if desired. Although the formation of a single device 100 is shown, it should be appreciated that the device 100 can be one device in an array of electrochromic devices, which can be formed concurrently.
FIG. 3A shows that a substrate 10 is provided. An insulating layer 11 is formed over the substrate 10. Referring to FIG. 3B, a first electrode 21 is formed over the insulating layer 11. The first electrode may be any suitable conductive material and is preferably tungsten. A layer of electrochromic material 30 is formed over the first electrode 21. The electrochromic material layer 30 is a layer of germanium-selenide-manganese. The germanium-selenide-manganese layer 30 is formed having a stoichiometry of (GexSe100-x)100-yMny, where x is less than or equal to about 30 and y is less than or equal to about 10. According to one embodiment of the invention, the germanium-selenide-manganese has a stoichiometry of about Ge20.2Se70.8Mn9.0. The layer 30 is about 450 Angstroms (Å) thick. A second electrode 22 is formed over the layer 30. The second electrode is preferably formed comprising silver and having a thickness of about 200 Å thick. Each of the electrodes 21, 22 and layer 30 can be formed more preferably by evaporation techniques.
Alternatively, as shown in FIG. 3C, the electrodes 21, 22 and layer 30 can be formed within a via 301, which is formed within the insulating layer 11.
Additional processing steps can be performed to complete the device 100 to achieve the structure shown in FIG. 1. For example, additional insulating layer can be formed to isolate the device 100 from other devices formed on the substrate 10 and connections to the voltage supply 25 can be formed. Additionally, one or more of the first electrode 21, second electrode 22, and layer 30 can be patterned as desired. For example, where the device 100 is to be used in a display device, one or more of the first electrode 21, second electrode 22, and layer 30 can be patterned to obtain the electrochromic behavior for the desired portion of the device 100.
FIG. 4 illustrates a processor system 300, which includes an electrochromic device 100 constructed according to the invention. The processor system 400, which can be, for example, a computer system, generally comprises a central processing unit (CPU) 444, such as a microprocessor, a digital signal processor, or other programmable digital logic devices, which communicates with an input/output (I/O) device 446 over a bus 452. The I/O device 446 includes a display device 410, which includes at least one electrochromic device 100. A memory circuit 448 communicates with the CPU 444 over bus 452, typically through a memory controller.
In the case of a computer system, the processor system 400 may include peripheral devices such as a floppy disk drive 454 and a compact disc (CD) ROM drive 456, which also communicate with CPU 444 over the bus 452. If desired, the memory circuit 448 may be combined with the processor, for example CPU 444, in a single integrated circuit.
The above description and drawings are illustrative of exemplary embodiments, which achieve the features and advantages of the present invention, but are not inclusive of all possible embodiments. Modification and substitutions to specific process conditions and structures can be made without departing from the spirit and scope of the present invention. Accordingly, the invention is not to be considered as being limited by the foregoing description and drawings, but is only limited by the scope of the appended claims.

## Claims

1. An electrochromic device comprising:
first and second electrodes; and
a layer of (GexSe100-x)100-yMny between the first and second electrodes,
wherein a color of said layer of (GexSe100-x)100-yMny changes in accordance with a voltage applied to said first and second electrodes.

2. The device of claim 1, wherein the (GexSe100-x)100-yMny layer is about 450 Å thick.

3. The device of claim 1, wherein the second electrode comprises silver and is about 200 Å thick.

4. The device of claim 1, wherein the first electrode comprises tungsten.

5. The device of claim 1, wherein x is less than or equal to about 30.

6. The device of claim 1, wherein y is less than or equal to about 10.

7. The device of claim 1, wherein the (GexSe100-x)100-yMny layer is a layer of Ge20.2Se70.8Mn9.0.

8. The device of claim 1, wherein at least one of the first and second electrodes comprises silver.

9. An electrochromic device comprising:
a first electrode, the first electrode comprising tungsten;
a second electrode, the second electrode comprising silver and having a thickness of about 200 Å; and
a layer of Ge20.2Se70.8Mn9.0 having a thickness of about 450 Å between the first and second electrodes.

10. A processor system, the system comprising:
a processor; and
an electrochromic device coupled to the processor, the electrochromic device comprising:
first and second electrodes; and
a layer of (GexSe100-x)100-yMny between the first and second electrodes,
wherein a color of said layer of (GexSe100-x)100-yMny changes in accordance with a voltage applied to said first and second electrodes.

11. The system of claim 10, wherein the (GexSe100-x)100-yMny layer is about 450 Å thick.

12. The system of claim 10, wherein the second electrode comprises silver and is about 200 Å thick.

13. The system of claim 10, wherein the first electrode comprises tungsten.

14. The system of claim 10, wherein x is less than or equal to about 30.

15. The system of claim 10, wherein y is less than or equal to about 10.

16. The system of claim 10, wherein at least one of the first and second electrodes comprises silver.

17. A method of forming an electrochromic device, the method comprising the acts of:
forming first and second electrodes; and
forming a layer of (GexSe100-x)100-yMny between the first and second electrodes,
a color of said layer of (GexSe100-x)100-yMny changing in accordance with a voltage applied to said first and second electrodes.

18. The method of claim 17, wherein the (GexSe100-x)100-yMny layer is formed having a thickness of about 450 Å.

19. The method of claim 17, wherein the second electrode comprises silver and is formed having a thickness of about 200 Å.

20. The method of claim 17, further comprising the act of patterning one or more of the first electrode, second electrode and (GexSe100-x)100-yMny layer.

21. The method of claim 17, wherein the first electrode is formed comprising tungsten.

22. The method of claim 17, wherein the (GexSe100-x)100-yMny layer is formed such that x is less than or equal to about 30.

23. The method of claim 17, wherein the (GexSe100-x)100-yMny layer is formed such that y is less than or equal to about 10.

24. The method of claim 17, wherein the act of forming the (GexSe100-x )100-yMny layer comprises forming a layer of Ge20.2Se70.8Mn9.0.

25. The method of claim 17, wherein the act of forming the first and second electrodes, comprises forming at least one of the first and second electrodes comprising silver.

26. An electrochromic device comprising:
an insulating material, the insulating material formed over a substrate;
first and second electrodes, the first electrode overlying the insulating material and comprising tungsten, and the second electrode comprising silver; and
a layer of (GexSe100-x)100-yMny between the first and second electrodes,
wherein x is less than or equal to about 30 and y is less than or equal to about 10, and a color of said layer of (GexSe100-x)100-yMny changing in accordance with a voltage applied to said first and second electrodes.

27. The device of claim 26, further comprising a voltage source, the voltage source being coupled to the first and second electrodes.