HALIDE MATERIAL AND OPTICAL UNIT AND OPTOELECTRONIC DEVICE HAVING THE SAME
20220302393 · 2022-09-22
Assignee
Inventors
- Hao-Wu Lin (Hsinchu City, TW)
- Ho-Hsiu Chou (Hsinchu City, TW)
- Chih-Li Chang (Hsinchu City, TW)
- Chien-Yu Chen (Hsinchu City, TW)
- Lin Yang (Hsinchu City, TW)
Cpc classification
Y02E10/549
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
A halide material having general formula ArMAX is disclosed. The halide material can be processed to an optoelectronic film with a halogenated formamidine and a lead halide, and the optoelectronic film can be applied in the manufacture of an optoelectronic device like a perovskite laser or a PeLED. Experimental data have proved that, the fabricated optoelectronic film shows a property of photoluminescence (PL) peak wavelength adjustable. Moreover, the PL peak wavelength moves from 482 nm to 534 nm with the increase of the content of lead (Pb), halogen (X) and formamidine (FA) in the optoelectronic film Furthermore, experimental data have also indicated that, the fabricated optoelectronic film can be used as a blue emissive layer, a red emissive layer or a green emissive layer, thereby having a significant potential for application in optoelectronics industry.
Claims
1. A halide material, having a general formula ArMAX, and being represented by following structural formula I: ##STR00007## wherein MA means methylamine, and Ar being selected from a group consisting of substituted or unsubstituted C6-C30 aryl group , substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C6-C30 arylalkyl group, substituted or unsubstituted C6-C30 arylthio group, substituted or unsubstituted C5-C30 heteroaryl group, substituted or unsubstituted C5-C30 heteroaryloxy group, substituted or unsubstituted C5-C30 heteroarylthio group, and substituted or unsubstituted C5-C30 heteroarylalkyl group; wherein m is a positive integer less than 10; and wherein X is a halogen selected from a group consisting of Cl, Br and I.
2. The halide material of claim 1, having a molecular weight in a range between 300 and 800.
3. The halide material of claim 1, wherein the halide material is processed to a film included in an optoelectronic device, and the optoelectronic device being selected from a group consisting of perovskite laser and perovskite light-emitting diode (PeLED).
4. The halide material of claim 1, wherein the halide material is processed to a gain medium layer included in a perovskite laser.
5. The halide material of claim 1, wherein the halide material is processed to an emission layer included in a perovskite light-emitting diode (PeLED).
6. An optoelectronic film, being made of a halide material having a general formula ArMAX, a halogenated formamidine having a general formula FAX2, and a metal halide, and having a general formula (ArMA).sub.2FA.sub.n−1B.sub.nX1.sub.3n+1; wherein MA means methylamine, and Ar being selected from a group consisting of substituted or unsubstituted C6-C30 aryl group , substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C6-C30 arylalkyl group, substituted or unsubstituted C6-C30 arylthio group, substituted or unsubstituted C5-C30 heteroaryl group, substituted or unsubstituted C5-C30 heteroaryloxy group, substituted or unsubstituted C5-C30 heteroarylthio group, and substituted or unsubstituted C5-C30 heteroarylalkyl group; wherein B is a metal element selected from a group consisting of Pb, Sn, Ti, and Ge, X1 being a halogen selected from a group consisting of Cl, Br and I, and X2 being a halogen selected from a group consisting of Br and I; and wherein n is a positive integer in a range between 1 and 8.
7. The optoelectronic film of claim 6, wherein the halide material is represented by following structural formula I: ##STR00008## wherein m is a positive integer less than 10.
8. The optoelectronic film of claim 6, wherein the halide material has a molecular weight in a range between 300 and 800.
9. The optoelectronic film of claim 6, wherein the optoelectronic film is included in an optoelectronic device selected from a group consisting of perovskite laser and perovskite light-emitting diode (PeLED).
10. The optoelectronic film of claim 6, wherein the optoelectronic film is a gain medium layer included in a perovskite laser.
11. The optoelectronic film of claim 6, wherein the optoelectronic film is an emission layer included in a perovskite light-emitting diode (PeLED).
12. An optoelectronic device, characterized in that containing an optoelectronic film having a general formula (ArMA).sub.2FA.sub.n−1B.sub.nX1.sub.3n+1; wherein the optoelectronic film is made of a halide material having a general formula ArMAX, a halogenated formamidine having a general formula FAX2, and a metal halide; wherein MA means methylamine, and Ar being selected from a group consisting of substituted or unsubstituted C6-C30 aryl group , substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C6-C30 arylalkyl group, substituted or unsubstituted C6-C30 arylthio group, substituted or unsubstituted C5-C30 heteroaryl group, substituted or unsubstituted C5-C30 heteroaryloxy group, substituted or unsubstituted C5-C30 heteroarylthio group, and substituted or unsubstituted C5-C30 heteroarylalkyl group; wherein B is a metal element selected from a group consisting of Pb, Sn, Ti, and Ge, X1 being a halogen selected from a group consisting of Cl, Br and I, and X2 being a halogen selected from a group consisting of Br and I; and wherein n is a positive integer in a range between 1 and 8.
13. The optoelectronic device of claim 12, wherein the halide material has a molecular weight in a range between 300 and 800.
14. The optoelectronic device of claim 12, wherein the halide material is represented by following structural formula I: ##STR00009## wherein m is a positive integer less than 10.
15. The optoelectronic device of claim 12, wherein the optoelectronic device is a perovskite laser, and the optoelectronic film being a gain medium layer included in the perovskite laser.
16. The optoelectronic device of claim 12, wherein the optoelectronic device is a perovskite light-emitting diode (PeLED), and the optoelectronic film being an emission layer included in the PeLED.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] The invention as well as a preferred mode of use and advantages thereof will be best understood by referring to the following detailed description of an illustrative embodiment in conjunction with the accompanying drawings, wherein:
[0030]
[0031]
[0032]
[0033]
[0034]
[0035]
[0036]
[0037]
[0038]
[0039]
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0040] To more clearly describe a halide material for application in the manufacture of an optoelectronic device according to the present invention, embodiments of the present invention will be described in detail with reference to the attached drawings hereinafter.
[0041] The present invention discloses a halide material, which has a general formula ArMAX, and is represented by following structural formula I:
##STR00003##
[0042] In the structural formula I, MA means methylamine, and Ar is selected from a group consisting of substituted or unsubstituted C6-C30 aryl group , substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C6-C30 arylalkyl group, substituted or unsubstituted C6-C30 arylthio group, substituted or unsubstituted C5-C30 heteroaryl group, substituted or unsubstituted C5-C30 heteroaryloxy group, substituted or unsubstituted C5-C30 heteroarylthio group, and substituted or unsubstituted C5-C30 heteroarylalkyl group. For example, Ar is represented by following structural formula I-1:
##STR00004##
[0043] In the structural formula I-1, each of R11, R12, R13, R14, R15, and R16 can optionally be hydrogen, alkyl group, alkenyl group, alkynyl group, alkoxy group, heterocycloalkyl group, cycloalkenyl group, or heterocycloalkenyl group. However, in case of considering to reduce the value of m as well as making the halide material have a specific molecular weight, each of R11, R12, R13, R14, R15, and R16 can also optionally be aryl group, aryloxy group, arylalkyl group, arylthio group, heteroaryl group, heteroaryloxy group, heteroarylthio group, or heteroarylalkyl group. According to the present invention, m is a positive integer less than 10, such that the halide material has a molecular weight in a range between 300 and 800. Moreover, X is a halogen selected from a group consisting of Cl, Br and I.
Manufacturing Method of the Halide Material
[0044] For proving that the halide material represented by the forgoing structural formula I is indeed makeable, two manufacturing methods for the halide material are introduced thereinafter.
[0045] Subsequently, 1.0 mole of intermediate product A-3, 1.5 moles of hydroxylamine hydrochloride and 4.8 moles of NaOH are added into a round-bottomed flask, and then 4.5-mL ethanol and 0.96-mL water are added into the round-bottomed flask. After being stirred, the solution accommodated in the round-bottomed flask is heated to 120 degrees Celsius, and is then kept at 120 degrees Celsius for 10 minutes. Subsequently, the solution is cooled down to room temperature, and then is constantly stirred for 3 hours. After that, 100-mL HCl solution (1M) is added in to the round-bottomed flask, and then the solution accommodated in the round-bottomed flask is applied with a suction filtration process. As a result, a white powder is obtained with up to 87% yield, where the white powder is (Z)-[1,1′:3′,1″-terphenyl]-4-carbaldehyde oxime (i.e., intermediate product A-4).
[0046] Next, 1.0 mole of intermediate product A-4 and 14 moles of Zinc (Zn) are added into a round-bottomed flask, and then 5.4-mL acetic acid is added into the round-bottomed flask. After being stirred, the solution accommodated in the round-bottomed flask is kept at room temperature for 16 hours. Thereafter, the solution accommodated in the round-bottomed flask is applied with a suction filtration process. Next, after alkaline water is added in to the solution, dichloromethane and water are used to extract the solution, thereby collecting organic fraction. Subsequently, magnesium sulfate anhydrous (MSDS) is adopted for to achieving a dewatering process of the organic fraction, and then hydrogen halide (e.g., HI) solution is added into the solution, so as to make white powder be precipitated in the round-bottomed flask. The white powder is 3PhMAX (e.g., 3PhMAI).
[0047] As explained in more detail, full names of reactants, intermediate products and end product 3PhMAX in
TABLE-US-00001 TABLE (1) Full name A-1 1-bromo-3-phenylbenzene A-2 4-Formylphenylboronic acid A-3 [1,1′:3′,1″-terphenyl]-4-carbaldehyde A-4 (Z)-[1,1′:3′,1″-terphenyl]-4-carbaldehyde oxime 3PhMAX [1,1′:3′,1″-terphenyl]-4-ylmethanammonium halide
[0048]
[0049] Subsequently, 1.1 mole of intermediate product A′-3, 1.0 mole of 4-Formylphenylboronic acid (i.e., reactant A′-4), 4.0 moles of K.sub.2CO.sub.3, and 0.1 mole of Pd(PPh.sub.3).sub.4 are added into a round-bottomed flask. Next, 3-mL THF and 3-mL water are further added into the round-bottomed flask. After being stirred, the solution accommodated in the round-bottomed flask is heated to 80 degrees Celsius, and is then kept at 80 degrees Celsius for 24 hours. Subsequently, the solution is cooled down to room temperature, and then dichloromethane and water are used to extract the solution, thereby collecting organic fraction. After that, magnesium sulfate anhydrous (MSDS) is used to achieve a dewatering process of the organic fraction, and then column chromatography machine and an eluent comprising ethyl acetate and n-hexane are adopted for purifying the dewatered organic fraction. As a result, creamy-white powder is obtained with up to 78% yield, where the creamy-white powder is [1,1′:3′,1″:3″′-quaterphenyl]-4-carbaldehyde (i.e., intermediate product A′-5).
[0050] Thereafter, as
[0051] Next, 1.0 mole of intermediate product A′-6 and 14 moles of Zn are added into a round-bottomed flask, and then 5.4-mL acetic acid is added into the round-bottomed flask. After being stirred, the solution accommodated in the round-bottomed flask is kept at room temperature for 16 hours. Thereafter, the solution accommodated in the round-bottomed flask is applied with a suction filtration process. Next, after alkaline water is added in to the solution, dichloromethane and water are used to extract the solution, thereby collecting organic fraction. Subsequently, magnesium sulfate anhydrous (MSDS) is adopted for to achieving a dewatering process of the organic fraction, and then hydrogen halide (i.e., HX) solution is added into the solution, so as to make white powder be precipitated in the round-bottomed flask. The white powder is 4PhMAX.
[0052] As explained in more detail, full names of reactants, intermediate products and end product 4PhMAX in
TABLE-US-00002 TABLE (2) Full name A′-1 biphenyl-3-boronic acid A′-2 1-bromo-3-iodobenzene A′-3 3-bromo-1,1′:3′,1″-terphenyl A′-4 4-Formylphenylboronic acid A′-5 [1,1′:3′,1″:3″,1′″-quaterphenyl]-4-carbaldehyde A′-6 (Z)-[1,1′:3′,1″:3″,1′″-quaterphenyl]-4-carbaldehyde oxime 4PhMAX [1,1′:3′,1″:3″,1′″-quaterphenyl]-4-ylmethanammonium halide
[0053]
##STR00005##
[0054] In the chemical structural formula I-2, Ar can be phenyl group, aryl group, aryloxy group, arylalkyl group, arylthio group, heteroaryl group, heteroaryloxy group, heteroarylthio group, or heteroarylalkyl group. Material engineers skilled in organic synthesis certainly know that the most basic aryl group is phenyl, and the notation of phenyl is “Ph”. Moreover, from
[0055] In
[0056] There are some exemplary embodiments for the halide material according to the present invention, and the exemplary embodiments are respectively represented by following chemical structural formulae (1)-(8):
##STR00006##
[0057] To describe the halide material repeatedly. According to present invention, the halide material has a general formula ArMAX, has a molecular weight in a range between 300 and 800, and is represented by the forgoing chemical structural formula I. In other words, the above-presented chemical structural formulae (1)-(8) are the exemplary embodiments of forgoing chemical structural formula I.
Photoelectric Unit Comprising the Halide Material
[0058] The present invention simultaneously discloses an optoelectronic film, which is made of a halide material having a general formula ArMAX, a halogenated formamidine having a general formula FAX2, and a metal halide, and has a general formula (ArMA).sub.2FA.sub.n−1B.sub.nX1.sub.3n+1. In one embodiment, the optoelectronic film of the present invention can be included in a perovskite laser for being used as a gain medium layer. In another one embodiment, the optoelectronic film of the present invention can also be included in a perovskite light-emitting diode (PeLED) for being used as an emission layer.
[0059]
Experiments
[0060] For proving that the optoelectronic film 10 of the present invention has a significant potential in application of the manufacture of photoelectric devices, experiment I is firstly competed. In experiment I, an optoelectronic film 10 made of 4PhMAI and PbI.sub.2 is formed on a substrate 20. Herein, it is found that the raw materials for making the optoelectronic film 10 in experiment I does not include halogenated formamidine (FAX2). Eventually, there are five samples of the optoelectronic film 10 fabricated in experiment I, and the basic information of the five samples are provided in following Table (3).
TABLE-US-00003 TABLE 3 Sample No. General formula 1 (4PhMA).sub.2PbI.sub.4 (n = 1) 2 (4PhMA).sub.2Pb.sub.2I.sub.7 (n = 2) 3 (4PhMA).sub.2Pb.sub.3I.sub.10 (n = 3) 4 (4PhMA).sub.2Pb.sub.4I.sub.13 (n = 4) 5 (4PhMA).sub.2Pb.sub.5I.sub.16 (n = 5)
[0061]
[0062] Moreover, for proving that the optoelectronic film 10 of the present invention has a significant potential in application of the manufacture of photoelectric devices, experiment II is also competed. In experiment I, an optoelectronic film 10 made of 4PhMAX (X=Br), FAX (X=Br) and PbBr.sub.2 is formed on a substrate 20. Herein, it is understood that optoelectronic film 10 formed on the substrate 20 has a general formula (4PhMA).sub.2FA.sub.n−1Pb.sub.nBr.sub.3n+1. Eventually, there are four samples of the optoelectronic film 10 fabricated in experiment II, and the basic information of the four samples are provided in following Table (4).
TABLE-US-00004 TABLE (4) Sample No. General formula 6 (n = 2) (4PhMA).sub.2FAPb.sub.2Br.sub.7 7 (n = 3) (4PhMA).sub.2FA.sub.2Pb.sub.3Br.sub.10 8 (n = 4) (4PhMA).sub.2FA.sub.3Pb.sub.4Br.sub.13 9 (n = 5) (4PhMA).sub.2FA.sub.4Pb.sub.5Br.sub.16
[0063]
TABLE-US-00005 TABLE (5A) Sample No. 6 Sample No. 7 PL peak wavelength 482 nm 522 nm FWHM 30 nm 34 nm PLQY 3.13% 9.03%
TABLE-US-00006 TABLE (5B) Sample No. 8 Sample No. 9 PL peak wavelength 530 nm 534 nm FWHM 26 nm 27 nm PLQY 39.6% 40.14%
[0064] From the experimental data of Table (2A) and Table (2B), it is clear that sample No. 6, 7, 8, and 9 have PL peak wavelength at 482 nm, 522 nm, 530 nm, and 434 nm, respectively. Therefore, experimental data have proved that, PL peak wavelength of the optoelectronic film 10 of the present invention not forward or backward shifts with the increase of n. Moreover, experimental data have also indicated that, the optoelectronic film 10 of the present invention can be used as a blue emissive layer, a red emissive layer or a green emissive layer, thereby having a significant potential for application in optoelectronics industry.
[0065] Therefore, through above descriptions, all embodiments and their constituting elements of the halide material for application in the manufacture of an optoelectronic device according to the present invention have been introduced completely and clearly. The above description is made on embodiments of the present invention. However, the embodiments are not intended to limit scope of the present invention, and all equivalent implementations or alterations within the spirit of the present invention still fall within the scope of the present invention.