Patent Application
20250179356
The present disclosure relates to a perovskite composite containing antimony trifluoride, an electronic element including the same, and a preparation method thereof.
Metal halide perovskite materials are used in optoelectronic devices to make the use of such optoelectronic devices efficient and stable. However, most perovskite optoelectronic devices are based on lead (Pb), and the commercial application thereof to various fields is challenging due to Pb toxicity and environmental hazards. Accordingly, there is a need to develop Pb-free perovskite materials to maintain improved optoelectronic device performance while avoiding environmental hazards.
Research has been conducted on tin halide perovskite as a Pb-free perovskite material. However, tin (Sn) is easily oxidized and may form undesirable electron traps. Additionally, the excessive hole concentration (>1018 cm−3) results in high p-type conductivity, making tin halide perovskite unsuitable to be used as a functional material for optoelectronic devices, which is problematic.
The present disclosure, which has been proposed to solve the problems described above, aims to provide a tin-based perovskite composite having a low hole concentration (≤1014 cm−1) and thus being usable for an optoelectronic device.
Additionally, the present disclosure aims to provide an optoelectronic device (for example, a transistor, a solar cell, a light-emitting diode, and the like) including the tin-based perovskite composite and thus having high stability.
According to a first aspect of the present disclosure, provided is a perovskite composite containing a tin (Sn)-based perovskite and antimony trifluoride (SbF3).
Additionally, the Sn-based perovskite may be doped with the SbF3.
Additionally, the Sn-based perovskite may be represented by Structural Formula 1 below.
A(1-a)(B(1-b)Cb)aSn(X(1-c)Yc)3 [Structural Formula 1]
In Structural Formula 1,
Additionally, the perovskite composite may contain 0.01 to 50 mol of the SbF3 based on 100 mol of the Sn-based perovskite.
Additionally, the perovskite composite may further contain tin fluoride (SnF2), and the Sn-based perovskite may be co-doped with the SbF3 and the SnF2.
Additionally, the perovskite composite may contain 0.01 to 50 mol of the SnF2 based on 100 mol of the Sn-based perovskite.
According to a second aspect of the present disclosure, provided is any one electronic element selected from the group consisting of a transistor, a solar cell, a light-emitting diode, a photodiode, and a photosensor, the electronic element including the perovskite composite.
According to a third aspect of the present disclosure, provided is a perovskite transistor including a gate electrode, an insulating layer disposed on the gate electrode, an active layer disposed on the insulating layer, the active layer including a perovskite composite containing a tin (Sn)-based perovskite and antimony trifluoride (SbF3), and a source electrode and a drain electrode spaced from each other while being disposed on the active layer.
Additionally, the Sn-based perovskite may be doped with the SbF3.
Additionally, the Sn-based perovskite may be represented by Structural Formula 1 below.
A(1-a)(B(1-b)Cb)aSn(X(1-c)Yc)3 [Structural Formula 1]
In Structural Formula 1,
Additionally, the perovskite composite may contain 0.01 to 50 mol of the SbF3 based on 100 mol of the Sn-based perovskite.
Additionally, the perovskite composite may further contain tin fluoride (SnF2), and the Sn-based perovskite may be co-doped with the SbF3 and the SnF2.
Additionally, the perovskite composite may contain 0.01 to 50 mol of the SnF2 based on 100 mol of the Sn-based perovskite.
Additionally, the gate electrode may include one or more selected from the group consisting of n-doped silicon (Si), p-doped Si, gold (Au), silver (Ag), platinum (Pt), titanium (Ti), Aluminum (Al), tungsten (W), magnesium (Mg), calcium (Ca), ytterbium (Yb), chromium (Cr), nickel (Ni), gold oxide, platinum oxide, silver oxide, palladium oxide, iron oxide, graphene, a carbon nanotube (CNT), an Ag nanowire (NW), indium tin oxide, and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), and the source electrode and the drain electrode may each independently include one or more selected from the group consisting of Au, Ag, Pt, Ti, Al, W, Mg, Ca, Yb, Cr, Ni, gold oxide, platinum oxide, silver oxide, palladium oxide, iron oxide, graphene, a CNT, an Ag NW, indium tin oxide, and PEDOT:PSS.
Additionally, the insulating layer may include one or more selected from the group consisting of silicon dioxide, glass, quartz, alumina, silicon carbide, magnesium oxide, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polystyrene (PS), polyimide (PI), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene (PE), silicon oxide (SiO2), germanium, alcohol polyvinyl (PVA), polymethyl methacrylate (PMMA), zirconium oxide (ZrO2), aluminum oxide (AlO2), and hafnium oxide (HfO2).
According to a fourth aspect of the present disclosure, provided is a method of preparing a perovskite composite, the method including the following steps: (a) preparing a mixed solution by mixing antimony trifluoride (SbF3) in a solution containing a compound represented by Structural Formula 2 below and a tin halide represented by Structural Formula 3 below, (b) preparing a perovskite precursor solution by heating the mixed solution, and (c) preparing a perovskite composite containing a tin (Sn)-based perovskite and the SbF3 by drying the perovskite precursor solution and then subjecting the dried perovskite precursor solution to heat treatment.
A(1-a)(B(1-b)Cb)a(X(1-c)Yc)1 [Structural Formula 2]
Sn(X(1-c)Yc)2 [Structural Formula 3]
In Structural Formulas 2 and 3,
Additionally, the Sn-based perovskite may be doped with the SbF3.
Additionally, the perovskite may be represented by Structural Formula 1 below.
A(1-a)(B(1-b)Cb)aSn(X(1-c)Yc)3 [Structural Formula 1]
In Structural Formula 1,
Additionally, the mixed solution may contain 0.01 to 50 mol of the SbF3 based on 100 mol of the Sn in the tin halide.
Additionally, the perovskite composite may further contain tin fluoride (SnF2), and the Sn-based perovskite may be co-doped with the SbF3 and the SnF2.
Additionally, the mixed solution may contain 0.01 to 50 mol of the SnF2 based on 100 mol of the Sn in the tin halide.
Additionally, Step (b) may be performed at a temperature in the range of 80° C. to 150° C.
Additionally, Step (c) may be performed at a temperature in the range of 100° C. to 150° C.
According to a fifth aspect of the present disclosure, provided is a method of manufacturing a perovskite transistor, the method including the following steps: (1) preparing a gate electrode/insulating layer stack including a gate electrode and an insulating layer disposed on the gate electrode, (2) forming an active layer including a perovskite composite containing a tin (Sn)-based perovskite and antimony trifluoride (SbF3) on the insulating layer, and (3) forming a source electrode and a drain electrode on the active layer.
A perovskite composite of the present disclosure is lead (Pb)-free by containing a tin (Sn)-based perovskite and antimony trifluoride (SbF3), has a low hole concentration (≤1014 cm−1), and thus can be used for an optoelectronic device.
Additionally, a perovskite transistor of the present disclosure includes the perovskite composite and thus can be highly stable.
These drawings are for the purpose of describing exemplary embodiments of the present disclosure, and the technical idea of the present disclosure thus should not be construed as being limited to the accompanying drawings:
Hereinafter, embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present disclosure.
However, the following description does not limit the present disclosure to specific embodiments. In the following description of the present disclosure, the detailed description of related arts will be omitted if it is determined that the gist of the present disclosure may be blurred.
Terms used herein are used only to describe specific embodiments and are not intended to limit the present disclosure. The singular expression includes the plural expression unless the context clearly indicates otherwise. It will be further understood that the terms “comprises”, “includes”, or “has” when used herein specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or combinations thereof.
Additionally, terms, such as “first”, “second”, etc. used herein, may be used to describe various components, but the components are not to be construed as being limited to the terms. These terms are used only for the purpose of distinguishing one component from another component. For example, without departing from the scope of the present disclosure, a first component may be referred to as a second component, and a second component may be also referred to as a first component.
Additionally, when a component is referred to as being “formed” or “laminated” on another component, it may be formed directly or attached to the front or one surface on the surface of the other component, but it will be understood that intervening elements may be present therebetween.
Hereinafter, a perovskite composite including antimony trifluoride, an electronic element including the same, and a preparation method thereof will be described in detail. However, these are disclosed only for illustrative purposes and are not meant to limit the present disclosure, and the scope of the present disclosure is only defined by the appended claims.
The present disclosure provides a perovskite composite containing a tin (Sn)-based perovskite and antimony trifluoride (SbF3).
Additionally, the Sn-based perovskite may be doped with the SbF3.
Additionally, the Sn-based perovskite may be represented by Structural Formula 1 below.
A(1-a)(B(1-b)Cb)aSn(X(1-c)Yc)3 [Structural Formula 1]
In Structural Formula 1,
Additionally, the perovskite composite may contain 0.01 to 50 mol of the SbF3, which is preferably in the range of 0.1 to 10 mol and more preferably in the range of 0.1 to 5 mol, based on 100 mol of the tin-based perovskite. When the amount of the SbF3 is less than 0.01 mol, an effect in hole concentration reduction obtained by containing SbF3 is insignificant, which is undesirable. When the amount of the SbF3 exceeds 50 mol, the effect is insignificant compared to the amount of SbF3 used, which is economically undesirable.
Additionally, the perovskite composite may further contain tin fluoride (SnF2), and the Sn-based perovskite may be co-doped with the SbF3 and the SnF2.
Additionally, the perovskite composite may contain 0.01 to 50 mol of the SnF2, which is preferably in the range of 0.1 to 10 mol and more preferably in the range of 0.1 to 5 mol, based on 100 mol of the Sn-based perovskite. When the amount of the SnF2 is less than 0.01 mol, an effect in hole concentration reduction obtained by containing SnF2 is insignificant, which is undesirable. When the amount of the SnF2 exceeds 50 mol, phase separation occurs due to the aggregation of SnF2, which is undesirable.
The present disclosure provides any one electronic element selected from the group consisting of a transistor, a solar cell, a light-emitting diode, a photodiode, and a photosensor, the electronic element including the perovskite composite.
Referring to 4A, the present disclosure provides a perovskite transistor including a gate electrode, an insulating layer disposed on the gate electrode, an active layer disposed on the insulating layer, the active layer including a perovskite composite containing a tin (Sn)-based perovskite and antimony trifluoride (SbF3), and a source electrode and a drain electrode spaced from each other while being disposed on the active layer.
Additionally, the Sn-based perovskite may be represented by Structural Formula 1 below.
A(1-a)(B(1-b)Cb)aSn(X(1-c)Yc)3 [Structural Formula 1]
In Structural Formula 1,
Additionally, the perovskite composite may contain 0.01 to 50 mol of the SbF3, which is preferably in the range of 0.1 to 10 mol and more preferably in the range of 0.1 to 5 mol, based on 100 mol of the tin-based perovskite. When the amount of the SbF3 is less than 0.01 mol, an effect in hole concentration reduction obtained by containing SbF3 is insignificant, which is undesirable. When the amount of the SbF3 exceeds 50 mol, the effect is insignificant compared to the amount of SbF3 used, which is economically undesirable.
Additionally, the perovskite composite may further contain tin fluoride (SnF2), and the tin-based perovskite may be co-doped with the SbF3 and the SnF2.
Additionally, the perovskite composite may contain 0.01 to 50 mol of the SnF2, which is preferably in the range of 0.1 to mol and more preferably in the range of 0.1 to 5 mol, based on 100 mol of the Sn-based perovskite. When the amount of the SnF2 is less than 0.01 mol, an effect in hole concentration reduction obtained by containing SnF2 is insignificant, which is undesirable. When the amount of the SnF2 exceeds 50 mol, phase separation occurs due to the aggregation of SnF2, which is undesirable.
Additionally, the gate electrode may include one or more selected from the group consisting of n-doped silicon (Si), p-doped Si, gold (Au), silver (Ag), platinum (Pt), titanium (Ti), Aluminum (Al), tungsten (W), magnesium (Mg), calcium (Ca), ytterbium (Yb), chromium (Cr), nickel (Ni), gold oxide, platinum oxide, silver oxide, palladium oxide, iron oxide, graphene, a carbon nanotube (CNT), an Ag nanowire (NW), indium tin oxide, and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS).
Specifically, the source electrode and the drain electrode may each independently include one or more selected from the group consisting of Au, Ag, Pt, Ti, Al, W, Mg, Ca, Yb, Cr, Ni, gold oxide, platinum oxide, silver oxide, palladium oxide, iron oxide, graphene, a CNT, an Ag NW, indium tin oxide, and PEDOT:PSS.
Additionally, the insulating layer may include one or more selected from the group consisting of silicon dioxide, glass, quartz, alumina, silicon carbide, magnesium oxide, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polystyrene (PS), polyimide (PI), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene (PE), silicon oxide (SiO2), germanium, polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), zirconium oxide (ZrO2), aluminum oxide (AlO2), and hafnium oxide (HfO2).
The present disclosure provides a method of preparing a perovskite composite, the method including the following steps: (a) preparing a mixed solution by mixing antimony trifluoride (SbF3) in a solution containing a compound represented by Structural Formula 2 below and a tin halide represented by Structural Formula 3 below, (b) preparing a perovskite precursor solution by heating the mixed solution, and (c) preparing a perovskite composite containing a tin (Sn)-based perovskite and the SbF3 by drying the perovskite precursor solution and then subjecting the dried perovskite precursor solution to heat treatment.
A(1-a)(B(1-b)Cb)a(X(1-c)Yc)1 [Structural Formula 2]
Sn(X(1-c)Yc)2 [Structural Formula 3]
In Structural Formulas 2 and 3,
Additionally, the tin-based perovskite may be doped with the SbF3.
Additionally, the perovskite may be represented by Structural Formula 1 below.
A(1-a)(B(1-b)Cb)aSn(X(1-c)Yc)3 [Structural Formula 1]
In Structural Formula 1,
Additionally, the mixed solution may contain 0.01 to 50 mol of the SbF3, which is preferably in the range of 0.1 to 10 mol and more preferably in the range of 0.1 to 5, based on 100 mol of Sn in the tin halide. When the amount of the SbF3 is less than 0.01 mol, an effect in hole concentration reduction obtained by containing SbF3 is insignificant, which is undesirable. When the amount of the SbF3 exceeds 50 mol, the effect is insignificant compared to the amount of SbF3 used, which is economically undesirable.
Additionally, the perovskite composite may further contain tin fluoride (SnF2), and the tin-based perovskite may be co-doped with the SbF3 and the SnF2.
Additionally, the mixed solution may contain 0.01 to 50 mol of the SnF2, which is preferably in the range of 0.1 to 10 mol and more preferably in the range of 0.1 to 5, based on 100 mol of Sn in the tin halide. When the amount of the SnF2 is less than 0.01 mol, an effect in hole concentration reduction obtained by containing SnF2 is insignificant, which is undesirable. When the amount of the SnF2 exceeds 50 mol, phase separation occurs due to the aggregation of SnF2, which is undesirable.
Additionally, Step (b) may be performed at a temperature in the range of 80° C. to 150° C. and is preferably performed at a temperature in the range of 90° C. to 110° C. When performing Step (b) at a temperature of lower than 80° C., the compounds contained in the mixed solution may fail to be well-mixed, thus deteriorating the performance of the perovskite composite, which is undesirable. When performing Step (b) at a temperature exceeding 150° C., by-products may be formed, which is undesirable.
Additionally, the heat treatment in Step (c) may be performed at a temperature in the range of 100° C. to 150° C. and is preferably performed at a temperature in the range of 120° C. to 140° C. When performing the heat treatment at a temperature of lower than 100° C., SbF3-doped perovskite may fail to be well-formed, which is undesirable. When performing the heat treatment at a temperature exceeding 150° C., by-products may be formed, which is undesirable.
The present disclosure provides a method of manufacturing a perovskite transistor, the method including the following steps: (1) preparing a gate electrode/insulating layer stack including a gate electrode and an insulating layer disposed on the gate electrode, (2) forming an active layer including a perovskite composite containing a tin (Sn)-based perovskite and antimony trifluoride (SbF3) on the insulating layer, and (3) forming a source electrode and a drain electrode on the active layer.
Hereinafter, the present disclosure will be described in more detail with examples. However, these examples are disclosed for illustrative purposes and the scope of the present disclosure is not limited thereby.
CsI and SnI2 were mixed at concentrations of 0.1 M and 5 M, respectively, in a co-solvent of N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). Then, a mixed solution was prepared such that the amount of antimony trifluoride (SbF3) was set to 1 mol in the resulting solution based on 100 mol of the total moles of tin ions (Sn2+) and antimony.
The resulting mixed solution was heated at a temperature in the range of room temperature to 100° C. for 0.1 to 24 hours, thereby preparing a precursor solution.
The precursor solution was dropped on a SiO2/Si substrate while performing spin coating one to five times at a speed of 0.5 to 9 kilo revolutions per minute (krpm) for 1 to 120 seconds. Next, heat treatment was performed at a temperature in the range of room temperature to 130° C. for 1 to 30 minutes, thereby preparing a perovskite composite.
Examples 1-2 and 1-3 were each independently prepared in the same manner as Example 1-1, except that the mixed solution is prepared by varying the concentration of SbF3 as shown in Table 1 below, instead of preparing the mixed solution so that the concentration of SbF3 was set to 1 mol %.
A perovskite composite was prepared in the same manner as Example 1-1, except that MAI was used instead of CsI.
Examples 2-2 and 2-3 were each independently prepared in the same manner as Example 1-1, except that MAI was used instead of CsI, and the mixed solution was prepared by varying the concentration of SbF3 as shown in Table 1 below, instead of preparing the mixed solution so that the concentration of SbF3 was set to 1 mol %.
A perovskite composite was prepared in the same manner as Example 1-1, except for using FAI instead of CsI.
Examples 2-2 and 2-3 were each independently prepared in the same manner as Example 1-1, except that FAI was used instead of CsI, and the mixed solution was prepared by varying the concentration of SbF3 as shown in Table 1 below, instead of preparing the mixed solution so that the concentration of SbF3 was set to 1 mol %.
Example 4-1 was prepared in the same manner as Example 1-1, except that the mixed solution was prepared by varying the concentrations of SbF3 and tin fluoride (SnF2) as shown in Table 1 below, instead of preparing the mixed solution so that the concentration of SbF3 was set to 1 mol %.
CsI and SnI2 were mixed at concentrations of 0.1 M and 5 M, respectively, in a co-solvent of DMF and DMSO. Then, a mixed solution was prepared such that the concentration of SnF2 was set to 1 mol % in the resulting solution based on 100 mol of the total moles of Sn2+ and SnF2.
The resulting mixed solution was heated at a temperature in the range of room temperature to 100° C. for 0.1 to 24 hours, thereby preparing a precursor solution.
The precursor solution was dropped on a SiO2/Si substrate while performing spin coating one to five times at a speed of 0.5 to 9 krpm for 1 to 120 seconds. Next, heat treatment was performed at a temperature in the range of room temperature to 130° C. for 1 to 30 minutes, thereby preparing a perovskite composite.
Comparative Examples 1-2 to 1-4 were each independently prepared in the same manner as Comparative Example 1-1, except that the mixed solution was prepared by varying the concentration of SnF2 as shown in Table 1 below, instead of preparing the mixed solution so that the concentration of SnF2 was set to 1 mol %.
First, the precursor solution prepared in Example 1 was dropped on SiO2 of a Si++/SiO2 substrate while performing spin coating one to five times at a speed of 0.5 to 9 krpm for 1 to 120 seconds. Next, heat treatment was performed at a temperature in the range of room temperature to 130° C. for 1 to 30 minutes, thereby forming an active layer including the perovskite composite.
An Au electrode was deposited on the active layer, thereby forming a source electrode and a drain electrode.
The transistors of Device Examples 2 to 4 and Device Comparative Examples 1 to 4 were manufactured under the same conditions as in Device Example 1 while varying the precursor solution used. The manufacturing conditions are shown in Table 2 below.
According to
According to
Specifically, when compared to the undoped perovskite composite of Comparative Example 1-4 (0 mol %), it is confirmed that the hole concentration in the case of Example 1-3, involving 4 mol % of SbF3, is enabled to be greatly reduced from 1018 cm−3 to 1014 cm−3. Additionally, when doped with SnF2, it is confirmed that 15 mol % of SnF2 is required to be used to make the hole concentration in the perovskite composite 1014 cm−3.
According to
Specifically, when co-doped with SbF3 and SnF2, it is confirmed that a portion of SnF2 is precipitated and functions as a heterogeneous nucleation site to promote nucleation and homogeneous growth of perovskite crystals, thus forming a uniform film.
According to
According to
According to 8A, it is confirmed that the perovskite transistor (5 mol % of SnF2+4 mol % of SbF3), according to Device Example 4, exhibits a small subthreshold swing (SS) of 0.5 V/dec and an ideal VON of about 0 V. A minimum gate voltage is required to turn the transistor on and off, so the VON of 0 V is significantly preferable for low-power consumption applications. SS is a measure of how efficiently a transistor can turn on and off, which is directly related to the electronic quality of the channel/dielectric interface. It is confirmed that the SS value in the case of Device Example 4 is much lower than that (≈5 V/dec) in the case of existing p-channel metal halide/oxide transistors with silicon oxide and is similar to that (≈0.5 V/dec) of n-channel metal-oxide transistors, such as indium gallium zinc oxide (IGZO) thin film transistor.
According to
The results of
According to
The scope of the present disclosure is defined by the appended claims rather than the detailed description presented above. All changes or modifications derived from the meaning and scope of the claims and the concept of equivalents should be construed to fall within the scope of the present disclosure.
A perovskite composite of the present disclosure is lead (Pb)-free by containing a tin (Sn)-based perovskite and antimony trifluoride (SbF3), has a low hole concentration (≤1014 cm−1), and thus can be used for an optoelectronic device.
Additionally, a perovskite transistor of the present disclosure includes the perovskite composite and thus can be highly stable.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0014547 | Feb 2022 | KR | national |
| 10-2022-0110804 | Sep 2022 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2022/019319 | 12/1/2022 | WO |
