U.S. patent application number 12/407950 was filed with the patent office on 2010-09-23 for electrochromic thin-film material.
Invention is credited to Jeremy A. Dixon, Paul P. Nguyen, Zhongchun Wang.
Application Number | 20100238535 12/407950 |
Document ID | / |
Family ID | 42737355 |
Filed Date | 2010-09-23 |
United States Patent
Application |
20100238535 |
Kind Code |
A1 |
Wang; Zhongchun ; et
al. |
September 23, 2010 |
ELECTROCHROMIC THIN-FILM MATERIAL
Abstract
One exemplary embodiment of an electrochromic thin-film material
comprises a metal-chalcogen compound; and/or a mixture or solid
solution of one or more metal-rich metal-chalcogen compounds and/or
lithium. One or more of the metals comprise Ti, Zr, Hf, V, Nb, Ta,
Cr, Mo, W, Mn, Sb, or Bi, or combinations thereof; and one or more
of the chalcogens comprise O, S, Se, or Te, or combinations
thereof.
Inventors: |
Wang; Zhongchun; (Santa
Rosa, CA) ; Nguyen; Paul P.; (San Jose, CA) ;
Dixon; Jeremy A.; (Santa Rosa, CA) |
Correspondence
Address: |
JOSEPH P. CURTIN
1469 N.W. MORGAN LANE
PORTLAND
OR
97229
US
|
Family ID: |
42737355 |
Appl. No.: |
12/407950 |
Filed: |
March 20, 2009 |
Current U.S.
Class: |
359/275 ;
252/583 |
Current CPC
Class: |
C09K 9/00 20130101 |
Class at
Publication: |
359/275 ;
252/583 |
International
Class: |
G02F 1/153 20060101
G02F001/153; C09K 9/00 20060101 C09K009/00 |
Claims
1. An electrochromic thin-film material, comprising a metal-rich
metal-chalcogen compound of at least one metal and at least one
chalcogen, in which an atomic ratio of a total amount of chalcogens
to a total amount of metals other than lithium is less than about
2:1.
2. The electrochromic thin-film material according to claim 1,
wherein the at least one metal comprises Ti, Zr, Hf, V, Nb, Ta, Cr,
Mo, W, Mn, Sb, or Bi, or combinations thereof.
3. The electrochromic thin-film material according to claim 2,
wherein the at least one chalcogen comprises O, S, Se, or Te, or
combinations thereof.
4. The electrochromic thin-film material according to claim 1,
wherein a thickness of the thin-film material is between about 1 nm
and about 1000 nm.
5. The electrochromic thin-film material according to claim 4,
wherein a thickness of the thin-film material is between about 5 nm
and about 50 nm.
6. The electrochromic thin-film material according to claim 1,
wherein the at least one chalcogen comprises O, S, Se, or Te, or
combinations thereof.
7. The electrochromic thin-film material according to claim 1,
wherein the thin-film material comprises Nb.sub.xTeLi.sub.y, in
which 0.5.ltoreq.x.ltoreq.20, and 0.ltoreq.y.ltoreq.20.
8. The electrochromic thin-film material according to claim 1,
wherein the thin-film material comprises Mo.sub.xTeLi.sub.y, in
which 0.5.ltoreq.x.ltoreq.20, and 0.ltoreq.y.ltoreq.20.
9. The electrochromic thin-film material according to claim 1,
wherein the thin-film material comprises Ti.sub.xTeLi.sub.y, in
which 0.5.ltoreq.x.ltoreq.20, and 0.ltoreq.y.ltoreq.20.
10. The electrochromic thin-film material according to claim 1,
wherein the thin-film material comprises W.sub.xTeLi.sub.y, in
which 0.5.ltoreq.x.ltoreq.20, and 0.ltoreq.y.ltoreq.20.
11. The electrochromic thin-film material according to claim 1,
wherein the thin-film material comprises Cr.sub.xTeLi.sub.y, in
which 0.5.ltoreq.x.ltoreq.20, and 0.ltoreq.y.ltoreq.20.
12. The electrochromic thin-film material according to claim 1,
wherein the thin-film material comprises
Sb.sub.xTeCo.sub.yLi.sub.z, in which 0.5.ltoreq.x.ltoreq.20,
0.01.ltoreq.y.ltoreq.20, and 0.ltoreq.z.ltoreq.20.
13. An all-solid-state electrochromic device, comprising: a
transparent base material; and an electrochromic multilayer-stack
structure formed on the transparent base material, the
electrochromic multilayer-stack structure comprising: a first
transparent-conductive film; an ion-storage layer formed on the
first transparent-conductive film; a solid-electrolyte layer formed
on the ion-storage layer; and an electrochromic layer formed on the
solid-electrolyte layer, the electrochromic layer comprising an
electrochromic thin-film material comprising a metal-rich
metal-chalcogen compound of at least one metal and at least one
chalcogen, in which an atomic ratio of a total amount of chalcogens
to a total amount of metals other than lithium is less than about
2:1.
14. The all solid-state electrochromic device according to claim
13, wherein the at least one metal comprises Ti, Zr, Hf, V, Nb, Ta,
Cr, Mo, W, Mn, Sb, or Bi, or combinations thereof.
15. The all solid-state electrochromic device according to claim
14, wherein the at least one chalcogen comprises O, S, Se, or Te,
or combinations thereof.
16. The all solid-state electrochromic device according to claim
13, wherein a thickness of the thin-film material is between about
1 nm and about 1000 nm.
17. The all solid-state electrochromic device according to claim
16, wherein a thickness of the thin-film material is between about
5 nm and about 50 nm.
18. The all solid-state electrochromic device according to claim
13, wherein the at least one chalcogen comprises O, S, Se, or Te,
or combinations thereof.
19. The all solid-state electrochromic device according to claim
13, wherein the thin-film material comprises at least one of
Nb.sub.xTeLi.sub.y, Mo.sub.xTeLi.sub.y, Ti.sub.xTeLi.sub.y,
W.sub.xTeLi.sub.y, or Cr.sub.xTeLi.sub.y, or combinations thereof,
in which 0.5.ltoreq.x.ltoreq.20, and 0.ltoreq.y.ltoreq.20.
20. The all solid-state electrochromic device according to claim
13, wherein the thin-film material comprises
Sb.sub.xTeCo.sub.yLi.sub.z, in which 0.5.ltoreq.x.ltoreq.20,
0.01.ltoreq.y.ltoreq.20, and 0.ltoreq.z.ltoreq.20.
Description
BACKGROUND
[0001] The subject matter disclosed herein relates to thin-film
materials that can be utilized in reflection-controllable
electrochromic windows (i.e., light-control glass) for buildings,
vehicles, aircraft and watercraft. More particularly, the subject
matter disclosed herein relates to reflection-controllable
electrochromic thin-film materials comprising a metal-chalcogen
compound in which one or more of the metals comprise Ti, Zr, Hf, V,
Nb, Ta, Cr, Mo, W, Mn, Sb, or Bi, or combinations thereof, and one
or more of the chalcogens comprise O, S, Se, or Te, or combinations
thereof.
[0002] Windows and other openings are generally the place where the
most heat enters and escapes buildings. For example, during the
winter about 48% of the heat produced by a heating system of a
building escapes through windows of the building. During the
summer, the proportion of heat that enters an air-conditioned room
through the windows can reach about 71%. A tremendous energy
savings can, therefore, be realized by effectively controlling
light and heat entering and escaping through windows. Light-control
glass has been developed to control the bi-directional flow of
light and heat through a window.
[0003] There are several ways that light is controlled by
light-control glass. One way is to form an electrochromic material
on the glass in which the transmissivity of the electrochromic
material reversibly changes upon application of a current or a
voltage. Another way is to form a thermochromic material on the
glass in which the transmissivity of the thermochromic material
changes with temperature. Yet another way is to use a gasochromic
material that changes its transmissivity by controlling the
atmosphere gas. Of these, electrochromic-based light-control glass
has been researched in which a tungsten-oxide thin film is used for
the light-control layer. Some commercial products based on this
type of electrochromic light-control glass have already
appeared.
[0004] Conventional electrochromic-based light-control glass,
including tungsten-oxide-based versions, all control light by
absorbing the light using a light-control layer. A drawback with
absorbing the light is that heat is produced and radiated into a
room when the light-control layer absorbs light, thereby
diminishing the energy-saving effect of the conventional
electrochromic light-control glass. To eliminate this drawback,
another approach of reflecting light rather than absorbing light
has been considered. Accordingly, a material capable of reversibly
switching between a mirror state and a transparent state would be
useful.
[0005] For a long time, such a material capable of switching
between a mirror state and a transparent state was not found, but
in 1996 a group in the Netherlands discovered a hydride of a rare
earth, such as yttrium or lanthanum, switches between a mirror
state and a transparent state under the influence of hydrogen. Such
a material is conventionally referred to as a "switchable mirror".
See, for example, J. N. Huiberts et al., Nature, 380, 1996, 231.
The rare-earth hydrides undergo a large change in transmissivity,
and have excellent light-control mirror characteristics.
Nevertheless, because a rare-earth element is used in the material,
there are problems in terms of resources and cost when
rare-earth-hydride-based switchable mirrors are used for window
coatings and other applications.
[0006] Additionally, conventional metal-hydride-based mirrors
suffer from poor cycle life due to the reactive nature of the metal
film, which is readily attacked by air or water. Notably, water is
one component of the electrolyte in electrochromic hydride mirrors,
and may be produced during removal of hydrogen from the mirror film
in both electrochromic and gasochromic devices. The life-cycle
degradation is conventionally inhibited by using additional barrier
layers for protecting the active materials and by sealing devices
for preventing access of environmental air and water. The former
approach of adding barrier layers is difficult to achieve and may
not be effective after long periods of use. The latter approach of
sealing does not address the problem of internal sources of water
or oxygen.
[0007] More recently, U.S. Pat. No. 6,647,166 B2 to T. J.
Richardson discloses alloys of magnesium and transitional-metals
that can be used as switchable-mirror materials, thereby
significantly reducing the cost of materials for
electrochromic-based light-control glass.
[0008] U.S. Pat. No. 7,042,615 B2 to T. J. Richardson discloses the
use of a semi-metal, such as antimony, as a switchable-mirror
thin-film material based on alloying and de-alloying of the
semi-metal with lithium: Sb+3Li.sup.++3e.sup.-=Li.sub.3Sb. Such
elements-based thin-film materials, however, suffer from several
severe drawbacks for the following reasons. (1) The electrochromic
reaction does not take place until very low potential (about 0.7 V
vs. Li/Li.sup.+), thus preventing the use of known transparent
conducting oxides, such as ITO and FTO, as the transparent
electrodes in an electrochromic device. (2) The reaction involves a
very large percentage of volume expansion/contraction upon full
lithiation/delithiation (about 136% for pure Sb), causing problems
of pulverization and de-lamination of the reflective layers. (3)
Low-resistivity metals (e.g., Ni and Co) need to be added to the
reflective layers to reduce the percentage of volume change and
increase the conductivity of the matrix, but the added metal
absorbs a significant portion of the incident light and lowers the
maximum transmission of an electrochromic window. (4) The
electrochromic reaction involving the extruding and re-admission of
the non-active metal is a non-topotactic and, thus, poorly
reversible reaction. (5) A direct-current voltage higher than about
4 V is needed to drive an electrochromic device employing such an
electrochromic material, which accelerates the degradation of an
electrochromic device during long-term use or cycling due to side
reactions associated with high driving-voltages.
[0009] Therefore, there is an urgent need in the electrochromic
fields to discover reflection-controllable electrochromic thin-film
materials based on intercalation compounds with intrinsic open
structures for highly reversible electro-optical switching at a
potential compatible with known transparent conducting oxide
electrodes.
[0010] In U.S. Pat. No. 7,042,615 B2, T. J. Richardson discloses
the use of transition-metal dichalcogenides (including TiS.sub.2,
NbSe.sub.2, and NbTe.sub.2) as switchable-mirror thin-film
materials, based on the contemplation that these semiconducting
solids become metallic upon lithium insertion or intercalation
(CATHODIC electrochromism). These chalcogen-rich transition-metal
chalcogenides, however, show too narrow electro-optical switching
ranges or too low coloration efficiencies, if any, to be useful in
practical electrochromic devices.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The subject matter disclosed herein is illustrated by way of
example and not by limitation in the accompanying figures in which
like reference numerals indicate similar elements and in which:
[0012] FIG. 1 graphically depicts UV-Vis-NIR transmittance and
reflectance spectra for 30-nm Nb.sub.3Te.sub.2 and
Nb.sub.3Te.sub.2Li.sub.0.4 thin films deposited on FTO-coated glass
substrates;
[0013] FIGS. 2A and 2B respectively depict the percentage
transmittance and reflection signal characteristics for the 30-nm
Nb.sub.3Te.sub.2 thin-film during wet cycling;
[0014] FIGS. 3A and 3B respectively depict the percentage
transmittance and reflection signal characteristics for the 30-nm
Nb.sub.3Te.sub.2Li.sub.0.4 thin-film during wet cycling;
[0015] FIG. 4 graphically depicts UV-Vis-NIR transmittance and
reflectance spectra for 30-nm Nb.sub.3Te.sub.2Li.sub.0.4 thin film
deposited at 275 degree Celsius on an ITO-coated glass
substrate;
[0016] FIGS. 5A and 5B respectively depict the percentage
transmittance and reflectance characteristics for the 30-nm
Nb.sub.3Te.sub.2Li.sub.0.4 thin-film deposited at 275 degree
Celsius during wet cycling;
[0017] FIG. 6 graphically depicts UV-Vis-NIR transmittance and
reflectance spectra for 30-nm MoTeLi.sub.0.2 thin film deposited on
an ITO-coated glass substrate;
[0018] FIGS. 7A and 7B respectively depict the percentage
transmittance and reflectance characteristics for the 30-nm
MoTeLi.sub.0.2 thin-film during wet cycling;
[0019] FIG. 8 graphically depicts UV-Vis-NIR transmittance spectra
for the 30-nm MoTeLi.sub.0.2 thin film at its colored and bleached
states;
[0020] FIG. 9 graphically depicts UV-Vis-NIR transmittance and
reflectance spectra for 30-nm Ti.sub.3Te.sub.2Li.sub.0.4 thin film
deposited on an ITO-coated glass substrate;
[0021] FIGS. 10A and 10B respectively depict the percentage
transmittance and reflection signal characteristics for the 30-nm
Ti.sub.3Te.sub.2Li.sub.0.4 thin-film during wet cycling;
[0022] FIG. 11 graphically depicts UV-Vis-NIR transmittance and
reflectance spectra for 30-nm W.sub.3Te.sub.2Li.sub.0.4 thin film
deposited on an ITO-coated glass substrate;
[0023] FIGS. 12A and 12B respectively depict the percentage
transmittance and reflectance characteristics for the 30-nm
W.sub.3Te.sub.2Li.sub.0.4 thin-film during wet cycling;
[0024] FIG. 13 graphically depicts UV-Vis-NIR transmittance spectra
for the 30-nm W.sub.3Te.sub.2Li.sub.0.4 thin film at its colored
and bleached states;
[0025] FIG. 14 graphically depicts UV-Vis-NIR transmittance and
reflectance spectra for 30-nm Cr.sub.3Te.sub.2Li.sub.0.4 thin film
deposited on an ITO-coated glass substrate;
[0026] FIGS. 15A and 15B respectively depict the percentage
transmittance and reflection signal characteristics for the 30-nm
Cr.sub.3Te.sub.2Li.sub.0.4 thin-film during wet cycling;
[0027] FIG. 16 graphically depicts UV-Vis-NIR transmittance and
reflectance spectra for 30-nm SbTeCo.sub.0.5Li.sub.0.4 thin film
deposited on 5-nm Cobalt-coated glass substrate;
[0028] FIGS. 17A and 17B respectively depicts the percentage
transmittance and reflection signal characteristics for the 30-nm
SbTeCo.sub.0.5Li.sub.0.4 thin film during wet cycling; and
[0029] FIG. 18 depicts an exemplary embodiment of a
multilayer-stack structure for a solid-state electrochromic device
that utilizes an electrochromic thin-film material according to the
subject matter disclosed herein.
DETAILED DESCRIPTION
[0030] As used herein, the word "exemplary" means "serving as an
example, instance, or illustration." Any embodiment described
herein as "exemplary" is not to be construed as necessarily
preferred or advantageous over other embodiments. The term
"topotactic" refers to solid-state reactions that are characterized
by the fact that defined lattice matrix elements specific to the
original solid phase remain unaltered in the course of the reaction
with respect to their structural organization. The term "chalcogen"
refers to any of the elements of O, S, Se, and Te. The term
"chalcogen-rich metal chalcogenide" refers to a metal chalcogenide
with a chalcogen/metal atomic ratio equal to or greater than about
2. The term "metal-rich metal chalcogenide" refers to a metal
chalcogenide with a chalcogen/metal atomic ratio less than about 2.
The abbreviation of "ITO" refers to "indium tin oxide", and the
abbreviation of "FTO" refers to "fluorine-doped tin oxide".
[0031] The subject matter disclosed herein relates to thin-film
materials that can be utilized in a reflection-controllable
electrochromic window (i.e., a light-control window) for
controlling the spectral transmissivity of the window of, for
example, a building, a vehicle, an aircraft and a watercraft,
without using blinds or curtains. More particularly, the subject
matter disclosed herein relates to highly durable
reflection-controllable electrochromic thin-film materials that can
be used as an electrochromically active layer. One exemplary
embodiment of a highly durable reflection-controllable
electrochromic thin-film material comprises metal-rich
metal-chalcogenide compounds that comprise tellurium, a transition
metal, and lithium. Another exemplary embodiment of a highly
durable reflection-controllable electrochromic thin-film material
comprises metal-rich metal-chalcogenide compounds that comprise
tellurium, a main-group metal, and lithium. Suitable transition
metals comprise Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn and
combinations thereof. Suitable main-group metals comprise Sb, Bi,
and mixture thereof. One exemplary embodiment of a metal-rich
metal-chalcogenide thin-film material comprising tellurium, a
transition metal, and lithium, has survived cycling tests in an
all-solid-state reflective device for over one thousand cycles with
the switching range of transmission degraded less than 10%.
[0032] The subject matter disclosed herein also relates to
thin-film materials that can also be utilized as anode materials in
thin-film lithium-ion batteries. One exemplary embodiment of a
metal-rich metal-chalcogenide thin-film material comprising
tellurium, a transition metal, and lithium, has exhibited a large
charge capacity (about 27000 Coulomb per cubic centimeter) and a
high reversibility (over 100 cycles) on charge-discharge cycling
between 1.0 V and 2.6 V versus Li.sup.+/Li.
[0033] In a highly reversible manner, the thin-film materials
disclosed herein become transparent upon lithiation, and become
reflective and/or absorptive upon delithiation.
[0034] The thin-film materials of metal-rich metal chalcogenides
disclosed herein show intense and highly reversible ANODIC
electrochromism. Specifically, the thin-film materials turn from
semi-metallic or metallic (reflective and/or absorptive) into
insulators (transparent) in a highly reversible manner upon lithium
insertion or intercalation.
[0035] Exemplary embodiments of a highly durable
reflection-controllable electrochromic thin-film metal-rich
metal-chalcogenide material comprise compounds of tellurium,
selenium, a transition metal, and lithium. The addition of selenium
into the metal-rich metal-chalcogenide material widens the optical
absorption band-gap of the material, and significantly increases
the visible-light transmittance of the thin-film material in its
bleached state. Addition of other chalcogen elements (such as O and
S) shows the same effect of optical band-gap widening. The optical
band-gap of the thin-film material increases with the
electronegativity of the constituent chalcogen elements in the
order of O>S>Se>Te.
[0036] The subject matter disclosed herein is described in specific
terms by several working examples in which a metal-rich
metal-chalcogenide thin film formed from one or more metals, one or
more chalcogens, and lithium was produced by co-sputtering in a
multi-source magnetron sputtering apparatus. The thin film for each
example was formed on a glass sheet substrate having a thickness of
about 3 mm. The glass sheet substrate was degreased, washed, dried,
placed in a vacuum apparatus, and then subjected to vacuum
evacuation. The thin film deposition took place in a high vacuum
chamber with a base pressure of about 3.times.10.sup.-7 Torr in the
plasma of argon at close to room temperature, except as otherwise
stated. The freshly deposited thin film had a typical metallic
gloss and was in a mirror state. It should be understood that the
subject matter disclosed herein is not limited by the following
several working examples.
[0037] In one exemplary embodiment of the subject matter disclosed
herein, a reflection-switchable thin-film material was formed by
co-sputtering Te and Nb at close to room temperature to form a
metal-rich metal-chalcogenide thin film having a composition of
Nb.sub.3Te.sub.2. Depending upon the embodiment, the thickness of
the thin film material formed can be between about 1 nm and about
500 nm. Curves 1 and 4 in FIG. 1 graphically depict UV-Vis-NIR
transmittance and reflectance spectra for a 30-nm Nb.sub.3Te.sub.2
thin film deposited on an FTO-coated glass substrate. Selection of
a particular thin-film material thickness is a tradeoff between a
relatively thin film, which provides a generally higher
transmittance, but a generally lower reflectance and durability,
and a relatively thick film, which provides a generally lower
transmittance, but a generally higher reflectance and better
durability. The optical switching characteristics of the 30-nm
Nb.sub.3Te.sub.2 thin film were evaluated by cycling it on a
potentiostat in a three-electrode electrochemical cell at 5 mV/s
between 1.0 V and 2.6 V vs. Li foil (Electrolyte: 1 M LiClO.sub.4
in propylene carbonate). The transmittance and reflectance of the
thin-film samples were simultaneously measured versus time during
cycling using a Si photo-detector, which is sensitive to photons in
the wavelength range of from about 400 nm to about 1100 nm. FIG. 2A
graphically depicts a plot of percentage transmittance versus time
for the 30-nm Nb.sub.3Te.sub.2 thin film during the wet cycling.
FIG. 2B graphically depicts a plot of reflection-signal intensity
versus time for the 30-nm Nb.sub.3Te.sub.2 thin film during the wet
cycling. As depicted in FIGS. 2A and 2B, the 30-nm Nb.sub.3Te.sub.2
thin film shows a large and persistent optical switching in both
transmission and reflection before degradation occurs after about
25 cycles.
[0038] In one exemplary embodiment of the subject matter disclosed
herein, a reflection-switchable thin-film material was formed by
co-sputtering Te, Nb and Li at close to room temperature to form a
lithiated metal-rich metal-chalcogenide thin film having a
composition of Nb.sub.3Te.sub.2Li.sub.0.4. Depending upon the
embodiment, the thickness of the thin film material formed can be
between about 1 nm and about 500 nm. Selection of a particular
thin-film material thickness is a tradeoff between a relatively
thin film, which provides a generally higher transmittance, but a
generally lower reflectance and durability, and a relatively thick
film, which provides a generally lower transmittance, but a
generally higher reflectance and better durability. Curves 2 and 3
in FIG. 1 graphically depict UV-Vis-NIR transmittance and
reflectance spectra for a 30-nm Nb.sub.3Te.sub.2Li.sub.0.4 thin
film deposited on an FTO-coated glass substrate. Compared to the
lithium-free sample shown by curves 1 and 4 in FIG. 1, the
lithium-containing sample shows slightly higher transmittance and
slightly lower reflectance. The optical switching characteristics
of the 30-nm Nb.sub.3Te.sub.2Li.sub.0.4 thin film were evaluated by
cycling it on a potentiostat in a three-electrode electrochemical
cell at 5 mV/s between 1.0 V and 2.6 V vs. Li foil (Electrolyte: 1
M LiClO.sub.4 in propylene carbonate). The transmittance and
reflectance of the thin-film sample were simultaneously measured
in-situ versus time during the wet cycling using a Si
photo-detector, which is sensitive to photons in the wavelength
range of from about 400 nm to about 1100 nm. FIG. 3A graphically
depicts a plot of percentage transmittance versus time for the
30-nm Nb.sub.3Te.sub.2Li.sub.0.4 thin film during the wet cycling.
FIG. 3B graphically depicts a plot of reflection-signal intensity
versus time for the 30-nm Nb.sub.3Te.sub.2Li.sub.0.4 thin film
during the wet cycling. Comparing the results depicted in FIGS. 3A
and 3B with the results depicted in FIGS. 2A and 2B, one can see
that the lithiated thin film shows a steadier optical switching in
both transmission and reflection. It should be understood that
other chalcogens and metals could be used to replace Te and Nb,
respectively, which are used in this exemplary embodiment of a
metal-rich metal-chalcogen thin-film material according to the
subject matter disclosed herein.
[0039] In one exemplary embodiment of the subject matter disclosed
herein, a reflection-switchable thin-film material was formed by
co-sputtering Te, Nb and Li onto an ITO-coated glass substrate
heated at about 275 degree Celsius to form a metal-rich
metal-chalcogenide thin film having a composition of
Nb.sub.3Te.sub.2Li.sub.0.4. Depending upon the embodiment, the
thickness of the thin film material formed can be between about 1
nm and about 500 nm. Selection of a particular thin-film material
thickness is a tradeoff between a relatively thin film, which
provides a generally higher transmittance, but a generally lower
reflectance and durability, and a relatively thick film, which
provides a generally lower transmittance, but a generally higher
reflectance and better durability. FIG. 4 graphically depicts
UV-Vis-NIR transmittance and reflectance spectra for a 30-nm
Nb.sub.3Te.sub.2Li.sub.0.4 thin film deposited at about 275 degree
Celsius on an ITO-coated glass substrate. Compared to the samples
deposited at close to room temperature as depicted in FIG. 1, the
sample deposited at an elevated temperature shows higher
transmittance in its as-deposited state. The optical switching
characteristics of the 30-nm Nb.sub.3Te.sub.2Li.sub.0.4 thin film
deposited at 275 degree Celsius was evaluated by cycling it on a
potentiostat in a three-electrode electrochemical cell at 5 mV/s
between 1.0 V and 2.6 V vs. Li foil (Electrolyte: 1 M LiClO.sub.4
in propylene carbonate). The transmittance and reflectance of the
thin-film sample were simultaneously measured in-situ versus time
during the wet cycling using a Si photo-detector, which is
sensitive to photons in the wavelength range of from about 400 nm
to about 1100 nm. FIG. 5A graphically depicts a plot of percentage
transmittance versus time for the 30-nm Nb.sub.3Te.sub.2Li.sub.0.4
thin film deposited at 275 degree Celsius during the wet cycling.
FIG. 5B graphically depicts a plot of percentage reflectance versus
time for the 30-nm Nb.sub.3Te.sub.2Li.sub.0.4 thin film deposited
at 275 degree Celsius during the wet cycling. Comparing the results
depicted in FIGS. 5A and 5B with the results depicted in FIGS. 3A
and 3B, it can be seen that the thin film deposited at an elevated
temperature shows narrower optical switching ranges in both
transmission and reflection, but shows much better durability for
extended cycling. It should be understood that other chalcogens and
metals could be used to replace Te and Nb, respectively, which are
used in this exemplary embodiment of a metal-rich metal-chalcogen
thin-film material according to the subject matter disclosed
herein.
[0040] In one exemplary embodiment of the subject matter disclosed
herein, a reflection-switchable thin-film material was formed by
co-sputtering Te with Mo and Li at close to room temperature to
form a metal-rich metal-chalcogenide thin film having a composition
of MoTeLi.sub.0.2. Depending upon the embodiment, the thickness of
the thin film material formed can be between about 1 nm and about
500 nm. FIG. 6 graphically depicts UV-Vis-NIR transmittance and
reflectance spectra for a 30-nm MoTeLi.sub.0.2 thin film deposited
on an ITO-coated glass substrate. Selection of a particular
thin-film material thickness is a tradeoff between a relatively
thin film, which provides a generally higher transmittance, but a
generally lower reflectance and durability, and a relatively thick
film, which provides a generally lower transmittance, but a
generally higher reflectance and better durability. The optical
switching characteristics of the 30-nm MoTeLi.sub.0.2 thin film
were evaluated by cycling it on a potentiostat in a three-electrode
electrochemical cell at 5 mV/s between 1.0 V and 2.6 V vs. Li foil
(Electrolyte: 1 M LiClO.sub.4 in propylene carbonate). The
transmittance and reflectance of the thin-film sample were
simultaneously measured in-situ versus time during the wet cycling
using a Si photo-detector, which is sensitive to photons in the
wavelength range of from about 400 nm to about 1100 nm. FIGS. 7A
and 7B respectively depict plots of percentage transmittance and
reflectance versus time for the MoTeLi.sub.0.2 thin film during the
wet cycling. The transmittance of the thin film switches between
about 5% and about 70%. Simultaneously, the reflectance ofthe thin
film at the wavelength of 550 nm switches between about 45% and
about 15%. The thin film shows excellent cyclibility with
negligible degradations seen after at least about one hundred
cycles. The spectral switching behaviors of the MoTeLi.sub.0.2 thin
film was measured using an Ocean Optics spectrophotometer. The thin
film was polarized at +1.0 V and 2.6 V vs. Li for 90 seconds before
recording the UV-vis-NIR transmittance spectra at its bleached and
colored states, respectively, as recorded in FIG. 8. The thin film
changes its transmittance at the wavelength of about 550 nm between
about 5.0% and about 45% within 90 seconds, thus demonstrating a
large range and a fast kinetics for its optical switching. It
should be understood that other chalcogens and metals could be used
to replace Te and Mo, respectively, which are used in this
exemplary embodiment of a metal-rich metal-chalcogen thin-film
material according to the subject matter disclosed herein.
[0041] In one exemplary embodiment of the subject matter disclosed
herein, a reflection-switchable thin-film material was formed by
co-sputtering Te with Ti and Li at close to room temperature to
form a metal-rich metal-chalcogenide thin film having a composition
of Ti.sub.3Te.sub.2Li.sub.0.4. Depending upon the embodiment, the
thickness of the thin film material formed can be between about 1
nm and about 500 nm. FIG. 9 graphically depicts UV-Vis-NIR
transmittance and reflectance spectra for a 30-nm
Ti.sub.3Te.sub.2Li.sub.0.4 thin film deposited on an ITO-coated
glass substrate. Selection of a particular thin-film material
thickness is a tradeoff between a relatively thin film, which
provides a generally higher transmittance, but a generally lower
reflectance and durability, and a relatively thick film, which
provides a generally lower transmittance, but a generally higher
reflectance and better durability. The optical switching
characteristics of the 30-nm Ti.sub.3Te.sub.2Li.sub.0.4 thin film
were evaluated by cycling it on a potentiostat in a conventional
three-electrode electrochemical cell at 5 mV/s between 1.0 V and
2.6 V vs. Li foil (Electrolyte: 1 M LiClO.sub.4 in propylene
carbonate). The transmittance and reflectance of the thin-film
sample were simultaneously measured in-situ versus time during the
wet cycling using a Si photo-detector, which is sensitive to
photons in the wavelength range of from about 400 nm to about 1100
nm. FIGS. 10A and 10B respectively depict plots of percentage
transmittance and reflection-signal intensity versus time for the
Ti.sub.3Te.sub.2Li.sub.0.4 thin film during the wet cycling. The
transmittance of the thin film switches between about 8% and about
60%. The thin film shows excellent cyclibility with negligible
degradations seen after at least about 50 cycles. It should be
understood that other chalcogens and metals could be used to
replace Te and Ti, respectively, which are used in this exemplary
embodiment of a metal-rich metal-chalcogen thin-film material
according to the subject matter disclosed herein.
[0042] In one exemplary embodiment of the subject matter disclosed
herein, a reflection-switchable thin-film material was formed by
co-sputtering Te with W and Li at close to room temperature to form
a metal-rich metal-chalcogenide thin film having a composition of
W.sub.3Te.sub.2Li.sub.0.4. Depending upon the embodiment, the
thickness of the thin film material formed can be between about 1
nm and about 500 nm. FIG. 11 graphically depicts UV-Vis-NIR
transmittance and reflectance spectra for a 30-nm
W.sub.3Te.sub.2Li.sub.0.4 thin film deposited on an ITO-coated
glass substrate. Selection of a particular thin-film material
thickness is a tradeoff between a relatively thin film, which
provides a generally higher transmittance, but a generally lower
reflectance and durability, and a relatively thick film, which
provides a generally lower transmittance, but a generally higher
reflectance and better durability. The optical switching
characteristics of the 30-nm W.sub.3Te.sub.2Li.sub.0.4 thin film
were evaluated by cycling it on a potentiostat in a three-electrode
electrochemical cell at 5 mV/s between 1.0 V and 2.6 V vs. Li foil
(Electrolyte: 1 M LiClO.sub.4 in propylene carbonate). The
transmittance and reflectance of the thin-film sample were
simultaneously measured in-situ versus time during the wet cycling
using a Si photo-detector, which is sensitive to photons in the
wavelength range of from about 400 nm to about 1100 nm. FIGS. 12A
and 12B respectively depict plots of percentage transmittance and
reflectance versus time for the W.sub.3Te.sub.2Li.sub.0.4 thin film
during the wet cycling. The transmittance of the thin film switches
between about 8% and about 60%. Simultaneously, the reflectance of
the thin film at the wavelength of 550 nm switches between about
32% and about 12%. The thin film shows excellent cyclibility with
negligible degradations seen after at least about one hundred
cycles. The spectral switching behaviors of the
W.sub.3Te.sub.2Li.sub.0.4 thin film was measured using an Ocean
Optics spectrophotometer. The thin film was polarized at +1.0 V and
2.6 V vs. Li for 90 seconds before recording the UV-vis-NIR
transmittance spectra at its bleached and colored states,
respectively, as depicted in FIG. 13. The thin film changes its
transmittance at the wavelength of about 550 nm between about 0.8%
and about 22% within 90 seconds, thus demonstrating a large range
and a fast kinetics for its optical switching. It should be
understood that other chalcogens and metals could be used to
replace Te and W, respectively, which are used in this exemplary
embodiment of a metal-rich metal-chalcogen thin-film material
according to the subject matter disclosed herein.
[0043] In one exemplary embodiment of the subject matter disclosed
herein, a reflection-switchable thin-film material was formed by
co-sputtering Te with Cr and Li at close to room temperature to
form a metal-rich metal-chalcogenide thin film having a composition
of Cr.sub.3Te.sub.2Li.sub.0.4. Depending upon the embodiment, the
thickness of the thin film material formed can be between about 1
nm and about 500 nm. FIG. 14 graphically depicts UV-Vis-NIR
transmittance and reflectance spectra for a 30-nm
Cr.sub.3Te.sub.2Li.sub.0.4 thin film deposited on an ITO-coated
glass substrate. Selection of a particular thin-film material
thickness is a tradeoff between a relatively thin film, which
provides a generally higher transmittance, but a generally lower
reflectance and durability, and a relatively thick film, which
provides a generally lower transmittance, but a generally higher
reflectance and better durability. The optical switching
characteristics of the 30-nm Cr.sub.3Te.sub.2Li.sub.0.4 thin film
were evaluated by cycling it on a potentiostat in a three-electrode
electrochemical cell at 5 mV/s between 1.0 V and 2.6 V vs. Li foil
(Electrolyte: 1 M LiClO.sub.4 in propylene carbonate). The
transmittance and reflectance of the thin-film sample were
simultaneously measured in-situ versus time during the wet cycling
using a Si photo-detector, which is sensitive to photons in the
wavelength range of from about 400 nm to about 1100 nm. FIGS. 15A
and 15B respectively depict the plots of percentage transmittance
and reflection-signal intensity versus time for the
Cr.sub.3Te.sub.2Li.sub.0.4 thin film during the wet cycling. The
transmittance of the thin film switches between about 8% and about
55%. The thin film shows excellent cyclibility with negligible
degradations seen after at least about 50 cycles. It should be
understood that other chalcogens and metals could be used to
replace Te and Cr, respectively, which are used in this exemplary
embodiment of a metal-rich metal-chalcogen thin-film material
according to the subject matter disclosed herein.
[0044] In one exemplary embodiment of the subject matter disclosed
herein, a reflection-switchable thin-film material was formed by
co-sputtering Te with Sb, Co, and Li at close to room temperature
to form a metal-rich metal-chalcogenide thin film having a
composition of SbTeCo.sub.0.5Li.sub.0.4. Depending upon the
embodiment, the thickness of the thin film material formed can be
between about 1 nm and about 500 nm. FIG. 16 graphically depicts
UV-Vis-NIR transmittance and reflectance spectra for a 30-nm
SbTeCo.sub.0.5Li.sub.0.4 thin film deposited on a 5-nm
cobalt-coated glass substrate. Selection of a particular thin-film
material thickness is a tradeoff between a relatively thin film,
which provides a generally higher transmittance, but a generally
lower reflectance and durability, and a relatively thick film,
which provides a generally lower transmittance, but a generally
higher reflectance and better durability. The optical switching
characteristics of the 30-nm SbTeCo.sub.0.5Li.sub.0.4 thin film
were evaluated by cycling it on a potentiostat in a three-electrode
electrochemical cell at 5 mV/s between 0.5 V and 2.1 V vs. Li foil
(Electrolyte: 1 M LiClO.sub.4 in propylene carbonate). The
transmittance and reflectance of the thin-film sample were
simultaneously measured in-situ versus time during the wet cycling
using a Si photo-detector, which is sensitive to photons in the
wavelength range of from about 400 nm to about 1100 nm. FIGS. 17A
and 17B respectively depict plots of percentage transmittance and
reflection-signal intensity versus time for the
SbTeCo.sub.0.5Li.sub.0.4 thin film during the wet cycling. The
transmittance of the thin film switches between about 12% and about
44%. The thin film shows excellent cyclibility with negligible
degradations seen after at least about 50 cycles. It should be
understood that other chalcogens and metals could be used to
replace Te, Sb and Co, respectively, which are used in this
exemplary embodiment of a metal-rich metal-chalcogen thin-film
material according to the subject matter disclosed herein.
[0045] FIG. 18 depicts an exemplary embodiment of a
multilayer-stack structure 1800 for a solid-state electrochromic
device that utilizes an electrochromic thin-film material according
to the subject matter disclosed herein. Exemplary multilayer-stack
structure 1800 comprises a transparent-conductive layer 1801, an
ion-storage layer 1802 formed in a well-known manner on
transparent-conductive layer 1801, a solid-electrolyte layer 1803
formed in a well-known manner on ion-storage layer 1802, an
electrochromic thin-film material layer 1804 formed in a well-known
manner on solid-electrolyte layer 1803, and a transparent
conductive layer 1805 formed on electrochromic thin-film material
layer 1804. In an alternative exemplary embodiment, an additional
sublayer of a base metal could be added between
transparent-conductive layer 1801 and ion-storage layer 1802 and/or
electrochromic thin-film 1804 and transparent-conductor layer 1805
to further increase the sheet conductance associated with a
transparent-conductor layers 1801 and/or 1805. Electrochromic
thin-film material layer 1804 is formed in accordance with the
subject matter disclosed herein. A protective layer formed from a
material that is non-permeable to lithium, oxygen, and water could
optionally be formed in a well-known manner over electrochromic
thin-film material layer 1804. Examples of suitable materials for
the protective layer include silicon oxide, aluminum oxide, silicon
aluminum oxide, zirconium oxide, silicon carbide, and silicon
oxycarbide. It should be understood that exemplary multilayer-stack
structure 1800 could be used in an exemplary electrochromic device
such as disclosed in co-pending and co-assigned U.S. patent Ser.
No. 12/242,917, entitled "Reflection-Controllable Electrochromic
Device Using a Base Metal as a Transparent Conductor," invented by
Z. Wang et al., filed Oct. 1, 2008, and incorporated by reference
herein. Additionally, electrical connections to exemplary
multilayer-stack structure 1800 are made in a well-known manner to
transparent-conductive layers 1801 and 1805, as respectively
depicted by electrical connections 1806 and 1807. It should be
understood that layers 1802 and 1804 could be physically
interchanged in structure 1800 without adversely affecting device
performance.
[0046] Although the foregoing disclosed subject matter has been
described in some detail for purposes of clarity of understanding,
it will be apparent that certain changes and modifications may be
practiced that are within the scope of the appended claims.
Accordingly, the present embodiments are to be considered as
illustrative and not restrictive, and the subject matter disclosed
herein is not to be limited to the details given herein, but may be
modified within the scope and equivalents of the appended
claims.
* * * * *