CN113394078A - Band gap adjustable MOFs electrode based on hexamercaptobenzene and preparation method thereof - Google Patents

Band gap adjustable MOFs electrode based on hexamercaptobenzene and preparation method thereof Download PDF

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CN113394078A
CN113394078A CN202110668242.8A CN202110668242A CN113394078A CN 113394078 A CN113394078 A CN 113394078A CN 202110668242 A CN202110668242 A CN 202110668242A CN 113394078 A CN113394078 A CN 113394078A
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electrode
silicon wafer
mofs
spin
electrode pattern
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王帅
董俊杰
陈欣
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Fudan University
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Abstract

The invention discloses a band gap adjustable MOFs electrode based on hexamercaptobenzene and a preparation method thereof. The method adopts a cleaned silicon wafer as a substrate, firstly sequentially spin-coats a sacrificial layer LOR3A and a photoresist S1813, and then etches a pre-designed electrode pattern on the silicon wafer by using a method of cleaning a developing solution after etching by a laser photoetching machine; putting the hexa-mercapto benzene solution and the metal salt solution into two electric air pump spray guns respectively, and alternately and uniformly spraying the two solutions on a silicon wafer with an electrode pattern by using the spray guns until continuous and uniform MOFs grow at the electrode position. And removing the photoresist outside the electrode after the electrode is prepared, thus obtaining the MOFs electrode. The MOFs electrode prepared by the invention has the carrier mobility of sigma = 0.001-0.1 cm2V− 1s−1. The invention can obtain electrodes with different band gaps by changing the metal types, and can be matched with semiconductor materials of different types.

Description

Band gap adjustable MOFs electrode based on hexamercaptobenzene and preparation method thereof
Technical Field
The invention belongs to the technical field of functional thin films, and particularly relates to a band gap adjustable MOFs electrode based on hexamercaptobenzene (BHT) and a preparation method thereof.
Background
Metal Organic Frameworks (MOFs), also called coordination polymers, are porous crystalline materials having an infinite network periodic structure formed by connecting a central Metal ion and an Organic ligand through a coordination bond. This concept was first proposed in 1995 by Yaghi. To date, more than 20000 MOFs materials with different compositions, crystal structures and morphologies have been reported. The MOFs material has huge development potential and application prospect in the fields of gas storage separation and storage, catalysis, sensors, biomedicine and the like because of the harmonious crystal structure and function, high porosity and huge specific surface area. Different central metal ions and coordinatable ligands create unique properties of metal organic framework compounds, so that the metal organic framework compounds have the characteristics of porosity, catalytic activity, structural diversity and the like.
Conductive MOFs are generally composed of conjugated ligands coordinated to a specific transition metal center, producing a large number of delocalized electrons on d-pi conjugated hybrid orbitals, and thus transported in an extended two-dimensional conductive network. Since the conductive MOFs obtained by coordination of metal and ligand have different structures, the energy level structures of the conductive MOFs are different, so that if the MOFs with different structures are used as electrodes, electrodes with different band gap structures can be obtained.
Disclosure of Invention
The invention aims to provide a novel band gap adjustable MOFs electrode and a preparation method thereof.
The MOFs with different band gap structures are obtained by changing the metal types, and can be matched with different types of semiconductor materials when being used as electrodes.
The band gap adjustable MOFs electrode provided by the invention is prepared from hexamercaptobenzene (BHT), and the preparation method comprises the following specific steps:
(1) cutting a silicon wafer into desired size and shape by using the silicon wafer as a substrate, and placing the cut silicon wafer in a container H2SO4And H2O2Soaking in the solution for more than 2 hours (such as 2-3 hours) to remove the impurities remained on the surface;
(2) spin-coating a sacrificial layer LOR3A (baking on a hot table for curing at 175 ℃ for 5min after spin-coating) and a photoresist S1813 (baking on the hot table for curing at 115 ℃ for 1min after spin-coating) on a cleaned silicon wafer by a spin coater in sequence, etching a pre-designed electrode pattern by a laser photoetching machine after cooling, then soaking for 30S-1 min by a developing solution, and simultaneously shaking the silicon wafer in a cross shape for developing, and then displaying the electrode pattern on the silicon wafer;
(3) preparing 5-20 mM ethanol solution of hexamercaptobenzene and 25-100 mM ethanol solution of metal salt, respectively placing the two solutions into two electric air pump spray guns, placing a silicon wafer with an electrode pattern on a hot table at a certain temperature (such as 85-95 ℃), and alternately and uniformly spraying the two solutions onto the electrode pattern of the silicon wafer by the spray guns until continuous and uniform MOFs (expressed as M-BHT) grows at the electrode position, wherein M is the metal. And after the electrode is prepared, removing the photoresist outside the electrode by using PG Remove to obtain the MOFs electrode.
A layer of semiconductor (such as DPP-DTT) is spin-coated on the prepared MOFs electrode, and the carrier mobility sigma = 0.001-0.01 cm is measured2V−1s−1。
In the present invention, the metal is preferably Ni or Cu.
The invention provides a preparation method of a band gap adjustable MOFs electrode, which can be used for preparing MOFs electrodes with different band gap structures by changing the type of metal.
Drawings
FIG. 1 is a schematic view of the structure of M-BHT electrodes (M means Ni and Cu).
FIG. 2 optical microscope schematic of M-BHT electrodes (M refers to Ni, Cu).
FIG. 3 is a graph of semiconductor performance for M-BHT electrodes (M refers to Ni, Cu).
Detailed Description
Example 1
Step 1: cutting the silicon wafer into pieces of desired size and shape, in H2SO4And H2O2(volume ratio is 2: 1) soaking the solution for more than 2 hours to remove the impurities remained on the surface;
step 2: spin-coating a sacrificial layer LOR3A (baking on a hot table at 175 ℃ for 5min after spin-coating) and a photoresist S1813 (baking on a hot table at 115 ℃ for 1 min) on a cleaned silicon wafer by a spin coater in sequence, cooling, etching a pre-designed electrode pattern by a laser photoetching machine, soaking for 1min by a developing solution, and developing by shaking the silicon wafer in a cross shape to obtain a silicon wafer with an etched electrode pattern;
and step 3: the 5 mM BHT/ethanol solution and 25 mM Cu (NO) were prepared3)2Respectively putting the two solutions into two electric air pump spray guns, putting a silicon wafer with an electrode pattern on a 90 ℃ hot table, and alternately and uniformly spraying the two solutions onto the electrode pattern of the silicon wafer by using the spray guns until continuous and uniform MOFs, which is marked as Cu-BHT, grows at the position of the electrode. And after the electrode is prepared, removing the photoresist outside the electrode by using PG Remove.
And 4, step 4: spin coating a layer of semiconductor DPP-DTT on the prepared MOFs electrode, and measuring the carrier mobility mu =0.0068 cm2V−1s−1。
Example 2
Step 1: cutting the silicon wafer into pieces of desired size and shape, in H2SO4And H2O2(volume ratio is 2: 1) soaking the solution for more than 2 hours to remove the impurities remained on the surface;
step 2: spin-coating a sacrificial layer LOR3A (baking on a hot table at 175 ℃ for 5min after spin-coating) and a photoresist S1813 (baking on a hot table at 115 ℃ for 1 min) on a cleaned silicon wafer by a spin coater in sequence, cooling, etching a pre-designed electrode pattern by a laser photoetching machine, soaking for 1min by a developing solution, and developing by shaking the silicon wafer in a cross shape to obtain a silicon wafer with an etched electrode pattern;
and step 3: the 5 mM BHT/ethanol solution and 25 mM NiCl solution were prepared2Respectively putting the two solutions into two electric air pump spray guns, putting a silicon wafer with an electrode pattern on a 90 ℃ hot table, and alternately and uniformly spraying the two solutions onto the electrode pattern of the silicon wafer by the spray guns until continuous and uniform MOFs, which are marked as Ni-BHT, grow at the electrode position. And after the electrode is prepared, removing the photoresist outside the electrode by using PG Remove.
And 4, step 4: spin coating a layer of semiconductor DPP-DTT on the prepared MOFs electrode, and measuring the carrier mobility mu =0.017 cm2V−1s−1。
Example 3
Step 1: cutting the silicon wafer into pieces of desired size and shape, in H2SO4And H2O2(volume ratio is 2: 1) soaking the solution for more than 2 hours to remove the impurities remained on the surface;
step 2: spin-coating a sacrificial layer LOR3A (baking on a hot table at 175 ℃ for 5min after spin-coating) and a photoresist S1813 (baking on a hot table at 115 ℃ for 1 min) on a cleaned silicon wafer by a spin coater in sequence, cooling, etching a pre-designed electrode pattern by a laser photoetching machine, soaking for 1min by a developing solution, and developing by shaking the silicon wafer in a cross shape to obtain a silicon wafer with an etched electrode pattern;
and step 3: the 20 mM BHT/ethanol solution and 100 mM Cu (NO) were prepared3)2Respectively putting the two solutions into two electric air pump spray guns, putting a silicon wafer with an electrode pattern on a 90 ℃ hot table, and alternately and uniformly spraying the two solutions onto the electrode pattern of the silicon wafer by using the spray guns until continuous and uniform MOFs, which is marked as Cu-BHT, grows at the position of the electrode. And after the electrode is prepared, removing the photoresist outside the electrode by using PG Remove.
And 4, step 4: spin coating a layer of semiconductor DPP-DTT on the prepared MOFs electrode, and measuring the carrier mobility mu =0.0182 cm2V−1s−1。
Example 4
Step 1: cutting the silicon wafer into pieces of desired size and shape, in H2SO4And H2O2(volume ratio is 2: 1) soaking the solution for more than 2 hours to remove the impurities remained on the surface;
step 2: spin-coating a sacrificial layer LOR3A (baking on a hot table at 175 ℃ for 5min after spin-coating) and a photoresist S1813 (baking on a hot table at 115 ℃ for 1 min) on a cleaned silicon wafer by a spin coater in sequence, cooling, etching a pre-designed electrode pattern by a laser photoetching machine, soaking for 1min by a developing solution, and developing by shaking the silicon wafer in a cross shape to obtain a silicon wafer with an etched electrode pattern;
and step 3: the 20 mM BHT/B is configuredAlcohol solution and 100 mM NiCl2Respectively putting the two solutions into two electric air pump spray guns, putting a silicon wafer with an electrode pattern on a 90 ℃ hot table, and alternately and uniformly spraying the two solutions onto the electrode pattern of the silicon wafer by the spray guns until continuous and uniform MOFs, which are marked as Ni-BHT, grow at the electrode position. And after the electrode is prepared, removing the photoresist outside the electrode by using PG Remove.
And 4, step 4: spin coating a layer of semiconductor DPP-DTT on the prepared MOFs electrode, and measuring the carrier mobility mu =0.033 cm2V−1s−1。

Claims (3)

1. A preparation method of a band gap adjustable MOFs electrode based on hexamercaptobenzene is characterized by comprising the following specific steps:
(1) cutting a silicon wafer into desired size and shape by using the silicon wafer as a substrate, and placing the cut silicon wafer in a container H2SO4And H2O2Soaking in the solution for more than 2 hours to remove the residual impurities on the surface;
(2) spin-coating a sacrificial layer LOR3A and a photoresist S1813 on a cleaned silicon wafer by using a spin coater in sequence, wherein the sacrificial layer LOR3A needs to be baked after being spin-coated to be cured, and the photoresist S1813 needs to be baked after being spin-coated to be cured; after cooling, etching a pre-designed electrode pattern by using a laser photoetching machine, then soaking the silicon wafer for 30 s-1 min by using a developing solution, meanwhile, shaking the silicon wafer in a cross shape for developing, and then displaying the electrode pattern on the silicon wafer;
(3) preparing 5-20 mM ethanol solution of hexamercaptobenzene and 25-100 mM ethanol solution of metal salt, respectively placing the two solutions into two electric air pump spray guns, placing a silicon wafer with an electrode pattern on a hot table, and alternately and uniformly spraying the two solutions onto the electrode pattern of the silicon wafer by the spray guns until continuous and uniform MOFs (metal organic frameworks) grow at the electrode position, wherein M is marked as M-BHT (butylated hydroxytoluene), and M is the metal; and after the electrode is prepared, removing the photoresist outside the electrode by using PG Remove to obtain the MOFs electrode.
2. The production method according to claim 1, wherein the metal is Ni or Cu.
3. The hexa-mercaptobenzene-based band gap-adjustable MOFs electrode prepared by the preparation method of claim 1 or 2 and having carrier mobility sigma = 0.001-0.01 cm2V−1s−1。
CN202110668242.8A 2021-06-16 2021-06-16 Band gap adjustable MOFs electrode based on hexamercaptobenzene and preparation method thereof Pending CN113394078A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114507357A (en) * 2022-03-21 2022-05-17 中国科学院化学研究所 Hexamercapto-silver benzene coordination polymer and preparation method thereof
CN115876994A (en) * 2022-11-18 2023-03-31 北京大学 DPP-DTT transistor biosensor, manufacturing method and detection method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111004403A (en) * 2019-11-05 2020-04-14 复旦大学 Method for in-situ growth of large-area Cu-BHT conductive thin film MOFs on silicon oxide surface
CN112661991A (en) * 2020-12-04 2021-04-16 复旦大学 Conductive MOFs thin film material prepared from tetramercaptobenzene and preparation method thereof
CN112679764A (en) * 2020-12-08 2021-04-20 复旦大学 Au/Ni-BHT heterojunction conductive MOFs thin film material and controllable preparation method thereof

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN111004403A (en) * 2019-11-05 2020-04-14 复旦大学 Method for in-situ growth of large-area Cu-BHT conductive thin film MOFs on silicon oxide surface
CN112661991A (en) * 2020-12-04 2021-04-16 复旦大学 Conductive MOFs thin film material prepared from tetramercaptobenzene and preparation method thereof
CN112679764A (en) * 2020-12-08 2021-04-20 复旦大学 Au/Ni-BHT heterojunction conductive MOFs thin film material and controllable preparation method thereof

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Title
XIN CHEN, YANG LU, JUNJIE DONG, ET AL.: "Ultrafast In Situ Synthesis of Large-Area Conductive Metal −Organic Frameworks on Substrates for Flexible Chemiresistive Sensing", 《ACS APPL. MATER. INTERFACES》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114507357A (en) * 2022-03-21 2022-05-17 中国科学院化学研究所 Hexamercapto-silver benzene coordination polymer and preparation method thereof
CN115876994A (en) * 2022-11-18 2023-03-31 北京大学 DPP-DTT transistor biosensor, manufacturing method and detection method

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Application publication date: 20210914