U.S. patent application number 16/033556 was filed with the patent office on 2020-01-16 for halide abx3 perovskite particles and their application in controlling photo-flux.
This patent application is currently assigned to 1-Material Inc. The applicant listed for this patent is 1-Material Inc. Invention is credited to Yanan Li, Shuyong Xiao, Dawei Zhang, Shiyong Zhao.
Application Number | 20200017364 16/033556 |
Document ID | / |
Family ID | 69139977 |
Filed Date | 2020-01-16 |
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United States Patent
Application |
20200017364 |
Kind Code |
A1 |
Li; Yanan ; et al. |
January 16, 2020 |
Halide ABX3 perovskite particles and their application in
controlling photo-flux
Abstract
The present invention provides a light valve containing
ABX.sub.3 perovskite particles; more specifically is related to a
light valve containing halide ABX.sub.3 perovskite particles that
can control light transmittance. The preferable halide ABX.sub.3
perovskite particles in this invention consist of A being at least
one of Cs.sup.+, CH3NH3.sup.+, and Rb.sup.+, B being at least one
of Pb.sup.2+, Ge.sup.2+, and Sn.sup.2+, and X being at least one of
Cl.sup.-, Br.sup.-, and I.sup.-. This kind of halide ABX.sub.3
perovskite particles were suspended in a liquid suspension to make
a light valve with a light transmittance control, which discloses a
completely new application for ABX.sub.3 perovskite materials.
Inventors: |
Li; Yanan; (Montreal,
CA) ; Zhang; Dawei; (Lachine, CA) ; Zhao;
Shiyong; (Longueuil, CA) ; Xiao; Shuyong;
(St-Laurent, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
1-Material Inc |
Dorval |
|
CA |
|
|
Assignee: |
1-Material Inc
Dorval
CA
|
Family ID: |
69139977 |
Appl. No.: |
16/033556 |
Filed: |
July 12, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C01G 19/006 20130101;
B82Y 20/00 20130101; C01P 2004/64 20130101; C01G 21/006 20130101;
G02F 1/155 20130101; C01P 2004/16 20130101; C01D 17/003 20130101;
C01P 2002/34 20130101; B82Y 30/00 20130101; C01G 17/006 20130101;
G02F 1/172 20130101 |
International
Class: |
C01D 17/00 20060101
C01D017/00; G02F 1/155 20060101 G02F001/155; G02F 1/17 20060101
G02F001/17 |
Claims
1. A light valve, comprising a first layer of a transparent
conductive substrate, an active layer containing ABX.sub.3
perovskite particles, and a second layer of transparent conductive
substrate, wherein said ABX.sub.3 perovskite particles have a
non-spherical morphology and are in a liquid suspension, and
wherein A is at least one of Cs.sup.+, CH.sub.3NH.sub.3.sup.+, and
Rb.sup.+; B is at least one of Pb.sup.2+, Ge.sup.2+, and Sn.sup.2+;
and X is at least one of Cl.sup.-, Br.sup.-, and I.sup.-; wherein
said ABX.sub.3 perovskite particles morphology is nanorods having
an average length of about 200 nm-500 nm, and an average diameter
of 50 nm-100 nm.
2. (canceled)
3. The light valve according to claim 1, wherein A is at least one
of Cs.sup.+ and CH.sub.3NH.sub.3.sup.+; B is Pb.sup.2+; X is at
least one of Br.sup.- and I.sup.-.
4. (canceled)
5. (canceled)
6. (canceled)
7. The light valve claim 1, wherein said halide ABX.sub.3
perovskite particles are uniformly dispersed in the liquid
suspension.
8. (canceled)
9. The light valve according to claim 7, wherein said liquid
suspension comprises one or more of a mineral resistive oil, a
synthetic resistive oil and a vegetable oil.
10. The light valve according to claim 7, wherein said liquid
suspension is sandwiched between two transparent electrodes.
11. A method of controlling light transmittance, comprising using
non-spherical ABX.sub.3 perovskite particles suspended in a liquid
suspension in a light control device, wherein said ABX.sub.3
perovskite particles are halide ABX.sub.3 perovskite particles, and
wherein A is at least one of Cs.sup.+, CH.sub.3NH.sub.3.sup.+, and
Rb.sup.+; B is at least one of Pb.sup.2+, Ge.sup.2+, and Sn.sup.2+;
and X is at least one of Cl.sup.-, Br.sup.-, and I.sup.-; wherein
said ABX.sub.3 perovskite particles morphology is nanorods having
an average length of about 200 nm-500 nm, and an average diameter
of 50 nm-100 nm.
12. The method according to claim 11, wherein the light control
device is a light valve.
Description
TECHNICAL FIELD
[0001] The present invention is related to ABX.sub.3 perovskite
particles and a light valve, more specifically is related to the
halide ABX.sub.3 perovskite particles and a light control valve
that can control the light transmission, and such a device is
preferably used for windows, lenses, or a light shutter such as a
sunroof. The fascinating multifunctional smart windows exhibit
promising features for a wide range of applications in buildings,
airplanes, automobiles, etc. The present invention provides a new
use for halide ABX.sub.3 perovskite material.
BACKGROUND ART
[0002] This invention presents the method to use halide ABX.sub.3
perovskite particles to control the flux of light in a light
control device, or referred as a light valve. Technically, a light
valve is a device that can regulate the amount of light passing
through a media like a water valve that can control the water flow.
Window shade can be viewed as a light valve too. However, in this
invention, the light valve is referred a device which can
electronically control the light transmittance, and such a device
is also scientifically referred as electrochromic device. Depending
on science behind an electrochromic device, it can be further
classified as polymer dispersed liquid crystal (PDLC) (U.S. patent
U.S. Pat. No. 3,585,381), electrochemical device (EC) (U.S. patent
U.S. Pat. No. 9,581,877) and suspension particles display (SPD)
(U.S. patents U.S. Pat. No. 6,606,185). Specifically, in this
invention, the light valve (LV for short hereafter) is referred a
device which the light transmittance can be controlled by
alternating current (AC). Such a device with controllable light
switching and energy-saving advantages can be used as smart
windows, rear-view car mirrors, displays, and so on.
[0003] Perovskite, the name of the perovskite, was originated from
the Russian geologist Perovski and originally single-pointed the
calcium titanate (CaTiO.sub.3) mineral. Later, crystals with
similar structures were collectively referred to as perovskites.
The cell structure of the ABX.sub.3 perovskite referred to in this
patent is shown in the FIG. 3. where `A` and `B` are two cations of
very different sizes, and `X` is an anion that bonds to both.
Specifically, in this invention, `A` is an alkaline cation or
organic ammonium, which has a positive charge, `B` is a transition
metal cation or an alkaline earth cation, which has two positive
charges; and `X` is a halide anion, which has a negative charge.
Among them, `B` cation and 6 `X` anions form octahedral units, and
8 octahedral units occupy the position of the hexahedral apex
centered on the `A` cation. This kind of material has a unique
structure, giving it excellent optical, electrical, magnetic and
thermodynamic properties, and is attracting increasingly studied
recently in many applications.
[0004] In 2009, the ABX.sub.3 perovskite material was first
reported for solar cells (J. Am. Chem. Soc. 131, 6050-6051, 2009).
"Science" rated perovskite solar cells as one of the top 10
scientific breakthroughs in 2013. In January 2018, the Swiss
Federal Institute of Technology in Lausanne sets new 23.25% the
world record efficiency of perovskite solar cells. In addition, the
ABX.sub.3 perovskite material has potential applications in LED
(Light Emitting Diodes) (Nature nanotechnology, 9: 687-692, 2014),
lasers (Nature Mater., 14: 636-642, 2015), photodetectors (Adv.
Materials, 30(8):1704333, 2018), memristors (Advanced Electronic
Materials, 2(7): 1600100, 2016).
[0005] However, in the prior art, there is no technology involving
making light valves using ABX.sub.3 perovskite materials.
[0006] Therefore, the present invention provides ABX.sub.3
perovskite particles and its application in a light valve, and
discloses a new application filed of the ABX.sub.3 perovskite
material.
SUMMARY OF THE INVENTION
[0007] This invention presents the method to use ABX.sub.3
perovskite particles to control the flux of light in a light
control device, or referred as a light valve. The present invention
provides a new use of the ABX.sub.3 perovskite material, and method
to make such a material. The present invention further provides a
light valve, comprising a liquid suspension having such a material
of ABX.sub.3 perovskite material, which can electronically control
transmission of light. More specifically, the ABX.sub.3 perovskite
particles, A is at least one of Cs.sup.+, CH3NH.sub.3.sup.+, and
Rb.sup.+, B is at least one of Pb.sup.2+, Ge.sup.2+, and Sn.sup.2/,
and X is at least one of Cl.sup.-, Br.sup.-, and I.sup.-. This
halide ABX.sub.3 perovskite is characterized in that have a
non-spherical morphology. The feature is that the halide ABX.sub.3
perovskite particles morphology is at least one of nanowires,
nanorods (one-dimensional); nanosheets (two-dimensional); cuboids,
irregular (three-dimensional) particles.
[0008] According to this invention, the liquid suspension, which is
used as a liquid medium to suspend the ABX.sub.3 perovskite
particles, comprises one or more a mineral resistive oil, a
synthetic resistive oil, and a vegetable oil.
[0009] According to this invention as illustrated in FIG. 1, the
said transparent electrode (100) can be made of the same material
or different materials, where light can be transmitted through,
preferably having a light transmittance equals to or greater than
80%.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 presents schematically the light controlling device,
wherein, a liquid suspension (300) is sandwiched between two
transparent substrates (100) and (100). The halide ABX.sub.3
perovskite particles (200) are suspended in the liquid suspension
(300).
[0011] FIG. 2 presents light transmittance of a light valve (LV)
device made according to this invention Example 6 before and after
applying an electric voltage of 220V.
[0012] FIG. 3 presents the cell structure of the ABX.sub.3
perovskite.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The present invention provides a new form of halide
ABX.sub.3 perovskite particles and the method to use them to
control the flux of light in a light control device, or referred as
a light valve.
[0014] FIG. 1 presents schematically the light controlling device,
wherein, a liquid suspension (300) is sandwiched between two
transparent substrates (100) and (100). The halide ABX.sub.3
perovskite particles (200) are suspended in the liquid suspension
(300). In the absence of an applied electrical field (OFF state),
the halide ABX.sub.3 perovskite particles in the liquid suspension
assume random positions due to Brownian movement. Hence, a beam of
light passing into the light valve is absorbed/scattered. The light
valve is thus relatively dark in the OFF state. When an electric
field is applied thereto (ON state), the light control halide
ABX.sub.3 perovskite particles are polarized, thereby being
arranged in directions parallel to each other in accordance with
the electric field, and most of the light can pass through the
cell. The light valve is thus relatively transparent in the ON
state.
[0015] The present invention provides a new use of the ABX.sub.3
perovskite particles, and method to make such a material. The
present invention further provides a light valve, comprising a
liquid suspension having such a material of ABX.sub.3 perovskite
particles, which can electronically control transmission of light.
More specifically, the ABX.sub.3 perovskite particles, A is at
least one of Cs.sup.+, CH3NH.sub.3.sup.+, and Rb.sup.+, B is at
least one of Pb.sup.2+, Ge.sup.2+, and Sn.sup.2+, and X is at least
one of Cl.sup.-, Br.sup.-, and I.sup.-. Sill more preferably, A is
at least one of Cs.sup.+ and CH3NH.sub.3.sup.+, B is Pb.sup.2+, X
is at least one of Br.sup.- and I.sup.-.
[0016] The halide ABX.sub.3 perovskite particles are characterized
in that have a non-spherical morphology. The feature is that the
halide ABX.sub.3 perovskite particles morphology is at least one of
the nanowires, nanorods (one-dimensional); nanosheets
(two-dimensional); cuboids, irregular (three-dimensional)
particles.
[0017] As illustrated in FIG. 1, the said ABX.sub.3 perovskite
particles (200) which are encapsulated inside the said liquid
suspension (300) shall be capable of re-orientating themselves in
an electronic field. In terms of geometric dimensions, the
ABX.sub.3 perovskite particles are preferably in a form of nanorods
having an average length of about 50 nm-2000 nm, more preferably
200 nm-500 nm, and an average diameter of 20 nm-200 nm, more
preferably 50 nm-100 nm.
[0018] According to this invention, the liquid suspension (300),
which is used as a liquid medium to suspend the ABX.sub.3
perovskite particles, comprises one or more non-aqueous,
electrically resistive liquids. Such a liquid or a liquid mixture,
referring as the suspension medium, can maintain the suspended
ABX.sub.3 perovskite particles in gravitational equilibrium.
[0019] More specifically in this invention, the liquid suspension
(300) comprises one or more a mineral resistive oil, a synthetic
resistive oil and a vegetable oil. Mineral resistive oils, such as
transformer oils; synthetic resistive oils, such as silicone oils,
fluorocarbon organic compounds, plasticizers (such as dioctyl
phthalate, dibutyl phthalate, diisobutyl phthalate, triisodecyl
trimellitate (TDTM), dodecylbenzene, polybutene oil; vegetable
oils, such as castor oil, soybean oil, rapeseed oil, are good
liquid suspension medium. Technically, the liquid suspension medium
used in the light valve of the present invention can be any liquid
light valve suspension known in the art and can be formulated
according to techniques well known to those skilled in the art.
[0020] According to this invention as illustrated in FIG. 1, the
said transparent electrode (100) can be made of the same material
or different materials, where light can be transmitted through,
preferably having a light transmittance equals to or greater than
80%, more preferably 90%. Either the said transparent electrode
(100) can be ITO conductive glass, ITO/PET conductive film, Ag
nanowire/PET conductive film, Cu nanowire/PET conductive film. The
transparent electrode (100) are preferred to be of the same
material for the simplicity of processing and for the same physical
properties (such as flexibility and thermal expansion), important
for device durability under certain conditions, such as thermal
stress.
[0021] As ABX.sub.3 perovskite particles are sensitive to moisture
and oxygen, the two transparent electrodes sandwiched by the liquid
suspension are sealed with a resistive material, such as epoxy
resin, etc., which can be used to seal the sealing material around
the two transparent electrodes. The light valve is driven by
alternating current to adjust light transmittance, preferably
5-500V alternating current.
[0022] The invention will now be described in more detail with
reference to the following examples. However, these examples are
given for illustration only and are not intended to limit the scope
of the present invention. All chemicals used in the examples are
purchased from Sigma-Aldrich Company unless otherwise specified. In
all these examples, all parts and percentages are by weight unless
otherwise noted. The light transmittance and absorption spectrum of
the LV device was measured by an Oceanview spectrometer.
Example 1 Preparation of Cs-Oleate
[0023] Cs.sub.2CO.sub.3 (4.07 g) was loaded into a 250 mL, 3-neck
flask along with octadecene (50 mL, ODE) and oleic acid (11.088 g),
and the mixture was dried for 1 h at 120.degree. C. and then heated
under Ar to 150.degree. C. until all Cs.sub.2CO.sub.3 reacted with
oleic acid. Since Cs-Oleate precipitates out of ODE at room
temperature, it has to be preheated to make it soluble before
usage.
Example 2 Synthesis of CsPbI.sub.3 Nanorods
[0024] N, N-dimethylformamide (100 mL, DMF) and PbI.sub.2 2.306 (5
mmol) were loaded into a 250 mL flask. Acetate acid 4.654 g (77.5
mmol) and dodecylamine 0.797 g (4.3 mmol) were added. After
complete solubilization of PbI.sub.2, 5 mL Cs-Oleate solution was
added (prepared as described Example 1). Then, the hybrid solution
was added into a 5 L flask along with 4200 mL toluene.
[0025] Then, centrifuge the reaction solution at 5000 G for 1.5
hours and discard the supernatant to yield the light control
CsPbI.sub.3.
[0026] Then, the CsPbI.sub.3 were further dispersed with 500 mL of
toluene, mixed well with shaking and sonication (referring as
LCP-Example-2).
Example 3 Synthesis of CsPbBr.sub.3 Nanorods
[0027] In the same manner as in Example 2, only 1.835 g of
PbBr.sub.2 was used instead of 2.306 g of PbI.sub.2. A toluene
mixture containing CsPbBr.sub.3 is referring as LCP-Example-3.
Example 4 Preparation of LV Suspension Containing CsPbI.sub.3
Nanorods
[0028] In the 250 ml round bottom glass flask was weighted 10 g of
TDTM (triisodecyltrimellitate), and the LCP-Example-2 prepared in
the Example 2 was added in portions. After thoroughly mixing by
shaking, toluene was subsequently removed by a rotary evaporator
for 3 hours at 80.degree. C. to yield a LV suspension containing
CsPbI.sub.3 referred as LV Suspension Example-4.
Example 5 Preparation of LV Suspension Containing CsPbBr.sub.3
Nanorods
[0029] In the 250 ml round bottom glass flask was weighted 15 g of
silicone oil, and the LCP-Example-3 prepared in the Example 3 was
added in portions. After thoroughly mixing by shaking, toluene was
subsequently removed by a rotary evaporator for 3 hours at
80.degree. C. to yield a LV suspension containing CsPbBr.sub.3
referred as LV Suspension Example-5.
Example 6 LV Devices Made from LV Suspension-Example-4
[0030] In this example, a wet thickness of 200 um of the LV
Suspension-Example 4 made in Example 4 was sealed between two
transparent electrodes of ITO conductive glass using epoxy resin to
produce a light valve referring as LV Device-6. When no electric
voltage is applied (OFF State), LV Device-6 exhibits an orange tint
and light transmission is measured to be 4.7%. When it was
electrically activated using 220 Volts AC at 50 Hz (ON State), the
LV Device-6 turns clearer and light transmission is measured to be
25.6%. FIG. 2 presents the absorption spectrum of LV Device-6 at
OFF state and ON state respectively.
Example 7 LV Devices Made from LV Suspension-Example-5
[0031] In this example, a wet thickness of 180 um of the LV
Suspension-Example 5 made in Example 5 was sealed between two
transparent electrodes of ITO conductive glass using epoxy resin to
produce a light valve referring as LV Device-7. When no electric
voltage is applied (OFF State), LV Device-7 exhibits an orange tint
and light transmission is measured to be 6.4%. When it was
electrically activated using 220 Volts AC at 50 Hz (ON State), the
LV Device-7 turns clearer and light transmission is measured to be
30.2%.
TABLE-US-00001 TABLE 1 Typical performance of LV devices
Transmittance % LV Device Off state On state LV Device-6 4.7 25.6
LV Device-7 6.4 30.2
TABLE-US-00002 U.S. PATENT DOCUMENTS 1. U.S. Pat. No. 3,585,381
Theodore L Hodson et al., 1969 2. U.S. Pat. No. 9,581,877 John
David Bass et al., 2015 3. U.S. Pat. No. 6,606,185 Robert L. Saxe,
2001 NON U.S. PATENT DOCUMENTS 1. J. Am. Chem. Soc., A. Kojima et
al., 2009 131: 6050-6051 2. Nature Nanotechnology, Tan, Zhi-Kuang,
et al., 2014 9: 687-692 3. Nature Mater., 14: 636-642 Haiming Zhu,
et al., 2015 4. Adv. Mater., 30(8): 1704333 Zhenqian Yang, et al.,
2018 5. Advanced Electronic Materials, Zhengguo Xiao, et al., 2016
2: 1600100
* * * * *