阅读说明：本技术 一种原子层沉积制备有机无机杂化卤素钙钛矿材料的方法 (Method for preparing organic-inorganic hybrid halogen perovskite material by atomic layer deposition ) 是由 丁士进 吴小晗 张卫 于 2019-11-12 设计创作，主要内容包括：本发明属于集成电路制造领域,其公开了一种原子层沉积制备有机无机杂化卤素钙钛矿材料的方法,该方法主要包括两部分：通过对材料基底进行3-氨基丙基三乙氧基硅烷(APTES)与氢碘酸或者十三氟辛基三乙氧基硅烷(FOTS)等表面处理,实现含铅前体的有效附着,能够形成一层单分子层；通入有机铵盐前体与单层含铅前体反应形成单层材料,多次循环得到最终的有机无机杂化卤素钙钛矿光电材料。本发明方法利用气相的原子层沉积方法,通过调控循环周期数进而得到所需厚度的薄膜材料,并且能够制备出大面积均匀的钙钛矿薄膜,从而拓展有机无机杂化卤素钙钛矿材料在太阳能电池、光探测器、激光器等光电领域的应用。(The invention belongs to the field of integrated circuit manufacturing, and discloses a method for preparing an organic-inorganic hybrid halogen perovskite material by atomic layer deposition, which mainly comprises two parts: the method comprises the following steps of (1) carrying out surface treatment on a material substrate such as 3-Aminopropyltriethoxysilane (APTES) and hydroiodic acid or tridecafluorooctyltriethoxysilane (FOTS), so that the lead-containing precursor is effectively attached, and a monolayer can be formed; and introducing an organic ammonium salt precursor to react with the single-layer lead-containing precursor to form a single-layer material, and recycling for multiple times to obtain the final organic-inorganic hybrid halogen perovskite photoelectric material. The method utilizes a gas-phase atomic layer deposition method, obtains the thin film material with the required thickness by regulating and controlling the cycle number, and can prepare the large-area uniform perovskite thin film, thereby expanding the application of the organic-inorganic hybrid halogen perovskite material in the photoelectric fields of solar cells, optical detectors, lasers and the like.)

1. A preparation method of an organic-inorganic hybrid halogen perovskite material is characterized by comprising the following steps: after the surface of the substrate is treated, sequentially introducing a lead-containing precursor and an organic ammonium salt precursor to obtain a single-layer organic-inorganic hybrid halogen perovskite material; and (3) repeatedly introducing a lead-containing precursor and an organic ammonium salt precursor, and determining the cycle number according to the required thickness to obtain the organic-inorganic hybrid halogen perovskite material.

2. The method according to claim 1, characterized in that it comprises in particular the steps of:

step 1, carrying out surface treatment on a substrate;

step 2, introducing a lead-containing precursor into a reaction cavity filled with the substrate subjected to surface treatment in a pulse mode until the lead-containing precursor is adsorbed to saturation on the surface of the substrate or reacts with active groups on the surface of the substrate to saturation;

step 3, introducing inert gas into the reaction chamber for purging;

step 4, introducing an organic ammonium salt precursor into the reaction cavity in a pulse mode until the organic ammonium salt precursor reacts with the lead-containing precursor on the surface of the substrate until the organic ammonium salt precursor is saturated;

step 5, introducing inert gas into the reaction cavity for purging to obtain a single-layer organic-inorganic hybrid halogen perovskite material;

and 6, repeating the steps 2-5, and determining the cycle times according to the required thickness to obtain the organic-inorganic hybrid halogen perovskite material.

3. The method of claim 1, wherein the substrate surface is treated with APTES followed by hydroiodic acid; or subjecting the substrate surface to FOTS treatment.

4. The method of claim 1, wherein the lead-containing precursor is any one of lead acetate, lead thiocyanate or lead bis (2,2,6,6, -tetramethyl-3, 5-heptanedionate).

5. The method as set forth in claim 1, wherein the lead-containing precursor is pulsed into the reaction chamber containing the surface-treated substrate after heating the reaction chamber to 100-150 ℃.

6. A method according to claim 1, wherein the vessel containing the lead-containing precursor and the organic ammonium salt precursor is heated to a temperature of 50 to 200 ℃.

7. The method of claim 1, wherein the substrate is a silicon-based substrate, an oxide substrate, a nitride substrate, a metal substrate, or a flexible polymer substrate.

8. An organic-inorganic hybrid halogen perovskite material obtained by the method according to any one of claims 1 to 7.

9. A product comprising the organic-inorganic hybrid halogen perovskite material of claim 8; preferably, the products are photovoltaic cells, lasers, light emitting diodes and light sensitive sensors.

10. The method of claims 1 to 7, the organic-inorganic hybrid halogen perovskite material of claim 8 or the product of claim 9 for use in the field of optoelectronics.

Technical Field

The invention belongs to the field of integrated circuit manufacturing, and relates to a method for preparing an organic-inorganic hybrid halogen perovskite photoelectric material by atomic layer deposition, which aims at large-scale, controllable and cyclicThe preparation of perovskite material with environmental compatibility, provides a gas phase atomic layer deposition technology, can realize the preparation of high-quality organic-inorganic hybrid halogen perovskite photoelectric material, such as methylamino lead iodide (CH)₃NH₃PbI₃) Lead formamidine iodide (FAPBI)₃) And the like.

Background

Since the discovery, organic-inorganic hybrid halogen perovskites have been gradually developed as an efficient and low-cost energy material. Such materials have many advantages: the forbidden bandwidth is compared and matched with the solar spectrum; the wide light absorption range is provided, and the full-spectrum absorption can be realized for visible light; the binding energy is small, generally less than 100 meV; a dual carrier material that can transport both electrons and holes; the diffusion length and the service life are longer, and the recombination probability of electrons and holes is low; the preparation method of the device is various and simple, and the characteristics determine that the material has very wide application prospect in the photoelectric field, such as photovoltaic cells, lasers, light emitting diodes and photosensitive sensors.

At present, the preparation methods of organic and inorganic hybrid halogen perovskite materials are mainly divided into three types: (1) the two-step solution method is that two precursors are respectively dissolved in an organic solvent, the lead-containing precursor is deposited to form a film, then the film is immersed in an organic ammonium salt solution, and finally the film is heated and annealed to be converted into a perovskite material; (2) one-step solution method, namely, two precursors are simultaneously dissolved in the same solvent, deposited on a substrate, and finally heated and annealed; (3) chemical vapor deposition. However, as the application of perovskite materials in the emerging fields of integrated circuits, detectors and the like is continuously expanded, higher requirements are provided for the thickness, uniformity, gap filling capability and the like of the film of the perovskite materials, however, the three methods for preparing the perovskite film are greatly limited, and the requirements of future photoelectric technology development cannot be met. In recent years, Atomic Layer Deposition (ALD) technology has been widely used in the field of integrated circuit fabrication, which benefits from the unique advantages of ALD technology, such as atomic layer-level thickness control capability, excellent conformal performance, large-area film uniformity, and precise digital thickness control capability. Thus, ALD provides a method for large-scale preparation of high-quality organic-inorganic hybrid halogen perovskite material thin films.

Disclosure of Invention

The invention aims to provide a preparation method of an organic-inorganic hybrid halogen perovskite photoelectric material, which adopts a gas-phase atomic layer deposition technology, ensures that a lead-containing precursor can be effectively adsorbed on the surface of a substrate to form a monomolecular layer through the specific modification of the substrate, and promotes the reaction of two perovskite precursors by high temperature assistance. The perovskite material with specific thickness and specific morphology is prepared by controlling the cycle number of growth, so that the controllable preparation of the perovskite material can be realized.

In order to achieve the purpose, the invention provides a method for preparing an organic-inorganic hybrid halogen perovskite photoelectric material by atomic layer deposition, which mainly comprises two parts: the effective adhesion of the lead-containing precursor can be realized by performing surface treatment on a material substrate such as 3-Aminopropyltriethoxysilane (APTES) and hydroiodic acid or tridecafluorooctyltriethoxysilane (FOTS), and a monolayer is formed; and introducing an organic ammonium salt precursor to react with the organic ammonium salt precursor to form a single-layer material, and recycling for multiple times to obtain the final organic-inorganic hybrid halogen perovskite photoelectric material.

Specifically, the technical scheme of the invention is as follows:

the invention discloses a preparation method of an organic-inorganic hybrid halogen perovskite material, which comprises the following steps: after the surface of the substrate is treated, sequentially introducing a lead-containing precursor and an organic ammonium salt precursor to obtain a single-layer organic-inorganic hybrid halogen perovskite material; and (3) repeatedly introducing a lead-containing precursor and an organic ammonium salt precursor, and determining the cycle number according to the required thickness to obtain the organic-inorganic hybrid halogen perovskite material.

The thickness is the final thickness of the organic-inorganic hybrid halogen perovskite material.

Preferably, the method specifically comprises the following steps:

step 1, carrying out surface treatment on a substrate;

step 2, introducing a lead-containing precursor into a reaction cavity filled with the substrate subjected to surface treatment in a pulse mode until the lead-containing precursor is adsorbed to saturation on the surface of the substrate or reacts with active groups on the surface of the substrate to saturation;

step 3, introducing inert gas into the reaction chamber for purging;

step 4, introducing an organic ammonium salt precursor into the reaction cavity in a pulse mode until the organic ammonium salt precursor reacts with the lead-containing precursor on the surface of the substrate until the organic ammonium salt precursor is saturated;

step 5, introducing inert gas into the reaction cavity for purging to obtain a single-layer organic-inorganic hybrid halogen perovskite material;

and 6, repeating the steps 2-5, and determining the cycle times according to the required thickness to obtain the organic-inorganic hybrid halogen perovskite material.

It should be understood that the steps of the present invention are not limited to the above steps, and other additional steps may be included before step 1, between step 1 and step 2, between step 2 and step 3, between step 3 and step 4, between step 4 and step 5, between step 5 and step 6, and after step 6, and are within the scope of the present invention.

Wherein, the purpose of purging by introducing inert gas in the step 3 is to remove the redundant lead-containing precursor in the reaction chamber.

And (5) introducing inert gas for purging in order to remove redundant organic ammonium salt and by-products generated by the reaction in the reaction chamber.

Preferably, APTES and hydroiodic acid are sequentially used for treating the surface of the substrate; or subjecting the substrate surface to FOTS treatment.

Preferably, the lead-containing precursor is any one of lead acetate, lead thiocyanate or lead bis (2,2,6,6, -tetramethyl-3, 5-heptanedionate).

It should be understood that the lead-containing precursor is not limited to the above, and one skilled in the art can select any suitable lead-containing precursor to implement the present invention according to the needs, and all such precursors are within the scope of the present invention.

Preferably, the organic ammonium salt precursor is any one selected from methyl ammonium iodide, formamidine ammonium iodide and isobutyl ammonium chloride.

It should be understood that the organic ammonium salt precursor is not limited to the above, and one skilled in the art can select any suitable organic ammonium salt precursor to implement the present invention according to the needs, and all such precursors are within the scope of the present invention.

Preferably, the vessel containing the lead-containing precursor and the organic ammonium salt precursor is heated to a temperature of 50 to 200 ℃.

More preferably, the lead-containing precursor is pulsed into the reaction chamber containing the surface-treated substrate after heating the reaction chamber to 100-150 ℃.

In some preferred embodiments of the present invention, the substrate of the present invention is described as single crystal silicon, but the present invention is not limited thereto, and the present invention can be applied to thin film deposition on silicon-based substrates, oxide substrates, nitride substrates, metal substrates, and flexible polymer substrates; while the substrate treatment of the present invention is described as APTES with hydroiodic acid or FOTS, other surface treatments can accomplish the same purpose; the growth method of the invention is described as the growth of organic-inorganic hybrid halogen lead-containing perovskite photoelectric materials, but the invention is also applicable to the growth of other all-inorganic perovskites and lead-free perovskite materials.

The second aspect of the invention discloses an organic-inorganic hybrid halogen perovskite material obtained by the method.

The third aspect of the invention discloses a product, which comprises the organic-inorganic hybrid halogen perovskite material; preferably, the products are photovoltaic cells, lasers, light emitting diodes and light sensitive sensors.

The fourth aspect of the invention discloses the application of the method, the organic-inorganic hybrid halogen perovskite material or the product in the photoelectric field.

On the basis of the common general knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily without departing from the concept and the protection scope of the invention.

The invention adopts the optical pulse assisted atomic layer deposition reaction, ensures that the lead-containing precursor is effectively attached to form a monolayer by depending on the specific treatment of the surface of the substrate, and promotes the two precursors to be effectively combined to form the organic-inorganic metal halide perovskite photoelectric material by utilizing high temperature. The perovskite material with a certain thickness is prepared by controlling the period number of the light pulse auxiliary growth, so that the thickness of the material can be controlled.

Compared with the prior art, the invention has the following advantages:

1) the method for preparing the organic-inorganic metal halide perovskite photoelectric material not only can easily realize the regulation and control of the thickness of the material, but also can prepare the material with a specific morphology.

2) The invention can regulate and control the composition of the material from the atomic layer level to prepare the perovskite material with different compositions.

3) The invention adopts a gas phase method, can ensure the compatibility of the material preparation environment, has small damage to the substrate, simultaneously does not introduce impurities into the film, and effectively improves the photoelectric property of the perovskite material.

Drawings

FIG. 1 is a schematic diagram of a reaction cycle for preparing an organic-inorganic hybrid halogen perovskite material according to the present invention.

FIG. 2 is a schematic diagram of APTES and hydroiodic acid treatment of substrates according to the present invention and adsorption of lead-containing precursors.

FIG. 3 is a schematic diagram of the present invention of the processing and adsorption of lead-containing precursors to substrate FOTS.

FIG. 4 is a schematic diagram of the growth of the organic-inorganic hybrid halogen perovskite material thin film prepared by the present invention.

FIG. 5 is a schematic diagram of organic-inorganic hybrid halogen perovskite materials with different morphologies prepared by combining photolithography and etching.

FIG. 6 is a schematic diagram of organic-inorganic hybrid halogen perovskite materials with different morphologies prepared by combining photolithography and etching.

Detailed Description

The technical solutions of the present invention are described in detail below with reference to the drawings and the embodiments, but the present invention is not limited to the scope of the embodiments.

The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions. The reagents and starting materials used in the present invention are commercially available.

In some preferred embodiments of the present invention, the following reaction formula (1) is methylammonium iodide (CH)₃NH₃I, MAI) and lead acetate (Pb (Ac)₂) Reaction to form perovskite CH₃NH₃PbI₃：

3CH₃NH₃I+Pb(Ac)₂→CH₃NH₃PbI₃+2CH₃NH₃Ac↑ (1)

In order to enable the reaction sources (lead acetate and methyl ammonium iodide) to generate enough vapor pressure, the container containing the lead acetate and the methyl ammonium iodide needs to be heated, and the heating temperature is preferably 50-80 ℃ and 150-180 ℃; in order to prevent the condensation of the reaction source in the transportation process, the transportation pipelines of the two precursors are also heated to the corresponding temperatures, namely 50-80 ℃ and 150-; to form the cubic perovskite material from the two precursors, the chamber is heated to 100-150 ℃.

FIG. 1 shows the growth of CH according to the present invention₃NH₃PbI₃A complete ALD growth cycle schematic diagram of the thin film comprises the steps of introducing a lead acetate precursor into a cavity to form a molecular layer on the surface of a substrate and introducing methyl ammonium iodide to form a perovskite material together with the lead acetate. The process specifically comprises the following steps:

s1, opening the cavity and the reaction source to heat, introducing a vapor phase lead acetate precursor into the reaction cavity, and allowing the lead source to stay in the reaction cavity for a period of time, so that lead source molecules are adsorbed on the surface of the substrate subjected to surface treatment or chemically react with the surface of the substrate, as shown in b in fig. 2 and b in fig. 3;

s2, introducing inert gas N into the reaction chamber₂Purging the lead source without surface adsorption, and leaving a monolayer of lead source with saturated surface adsorption, as shown in a in fig. 4;

s3, introducing methyl ammonium iodide into the cavity, and reacting with surface lead acetate molecules under the action of heating to generate a layer of perovskite material on the surface, as shown in a b diagram in figure 4.

S4，Introducing inert gas N into the reaction chamber₂The reaction by-products and excess methyl ammonium iodide source are purged clean, leaving a single layer of perovskite material. This completes ALD deposition of CH₃NH₃PbI₃One complete reaction cycle of the film.

S5, repeating S1-4 times n (n is 1, 2, 3 …) to obtain CH with a certain thickness₃NH₃PbI₃The film, as shown in fig. 4 c.

In the present invention, the surface treatment of the substrate is a key step for realizing the material preparation, and the substrate surface may be subjected to APTES treatment and then immersed in a hydriodic acid solution to make the substrate surface covered with a layer of ammonium salt, as shown in a in fig. 2, or subjected to FOTS treatment to make the substrate surface carry a layer of highly electronegative fluorine-containing molecules, as shown in a in fig. 3.

In the invention, different patterns can be obtained on the surface of the substrate by means of photoetching, etching and the like in the surface treatment process of the substrate, so that the adsorption position of the lead acetate monomolecular layer can be limited, and perovskite materials with different morphologies can be finally prepared, as shown in fig. 5-6.

In conclusion, the invention provides a method for preparing an organic-inorganic hybrid halogen perovskite photoelectric material by performing specific treatment on a substrate to realize atomic layer deposition. Compared with the material prepared by the traditional method, the perovskite material grown by the method has the property of controllable thickness, so that the regulation and control of photoelectric properties are realized; perovskite materials with different morphologies can be obtained by regulating and controlling the surface treatment process; mild preparation process, strong compatibility and the like.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.