Design and synthesis method based on semiconductor cluster photoresist

Abstract

The invention discloses a semiconductor cluster photoresist-based design and synthesis method, and relates to the technical field of semiconductor cluster photoresist design, and the semiconductor cluster photoresist-based design and synthesis method comprises the following steps: synthesizing a semiconductor cluster photoresist material; dissolving the semiconductor cluster material in an organic solvent to form a photoresist solution; coating a substrate with the photoresist solution to form a homogeneous film; performing selective exposure on the film through ultraviolet light or electron beams to realize patterning; removing the material in the unexposed area through a developing process to obtain a graphical structure; the semiconductor cluster is selected from at least one of InP (indium phosphide), ZnSe (zinc selenide), ZnS (zinc sulfide), InAs (indium arsenide), ZnTe (zinc telluride), CdSe (cadmium selenide), CdS (cadmium sulfide) or CdTe (cadmium The semiconductor cluster with a clear structure is used as a photosensitive unit, so that the integrated design of a photoetching function and a material function is realized, a photosensitizer does not need to be additionally added or complicated ligand modification does not need to be carried out, a synthesis path is simplified, the material purity is remarkably improved, and the prepared cluster photoresist can be directly patterned under ultraviolet or electron beam exposure.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of inorganic photoresist design, and particularly relates to a design and synthesis method of a semiconductor cluster photoresist. BACKGROUND

[0002] The inorganic photoresist design refers to a technology of developing and designing an inorganic material-based photoresist used in a microelectronic manufacturing process. The photoresist is a key material used for pattern transfer in a semiconductor manufacturing process, and can form an accurate circuit pattern in an exposure and development process. Traditional photoresists are mostly organic polymer materials, but as the size of semiconductor devices is continuously reduced, higher resolution, better thermal stability and chemical stability and other requirements are put forward for the photoresist.

[0003] In the field of inorganic photoresist design, the main components of traditional organic photoresists are high molecular resins (such as polyimide, polystyrene, PMMA) and photosensitizers (such as photoacid generators), which have been widely used in CMOS device manufacturing and microelectronic packaging fields. However, as the pattern size is continuously reduced, the resolution of such photoresists is limited, the thermal stability is poor, and the organic residues are difficult to remove, which limits their application in the next generation of devices. SUMMARY

[0004] In view of the above existing problems, the present application is proposed.

[0005] Therefore, the present application provides a design and synthesis method of a semiconductor cluster photoresist, which solves the problems of limited resolution, poor thermal stability and difficult removal of organic residues of the photoresist, and limits the application of the photoresist in the next generation of devices.

[0006] To solve the above technical problems, the present application provides the following technical solutions.

[0007] In a first aspect, the present application provides a design and synthesis method of a semiconductor cluster photoresist, which comprises:

[0008] Synthesizing a semiconductor cluster photoresist material;

[0009] Dissolving the semiconductor cluster material in an organic solvent to form a photoresist solution;

[0010] Coating the photoresist solution on a substrate to form a homogeneous thin film;

[0011] Selectively exposing the thin film to ultraviolet light or an electron beam to realize patterning;

[0012] Removing the material in the unexposed area through a development process to obtain a patterned structure;

[0013] The semiconductor cluster is selected from at least one of InP, ZnSe, ZnS, InAs, ZnTe, CdSe, CdS or CdTe.

[0014] As a preferred solution of the design and synthesis method of the semiconductor cluster-based photoresist according to the present application, wherein: the synthesis method of the semiconductor cluster comprises:

[0015] Preparation of metal precursor and anion precursor;

[0016] Under the protection of inert gas, the metal precursor and anion precursor are reacted in an organic solvent to generate semiconductor clusters;

[0017] The semiconductor clusters are separated by centrifugation and purification steps;

[0018] The characteristic absorption peak of the semiconductor cluster is confirmed by UV-Vis absorption spectrum characterization.

[0019] As a preferred solution of the design and synthesis method of the semiconductor cluster-based photoresist according to the present application, wherein: the synthesis method of the InP cluster comprises:

[0020] The indium myristate precursor is reacted with tris(trimethylsilyl) phosphine in toluene;

[0021] Ethane-1,2-diyl bis(4-azido-2,3,5,6-tetrafluorobenzoate) auxiliary dispersion is added;

[0022] The InP cluster is obtained by centrifugation and solvent purification, and its characteristic absorption peak is located at 398 nm.

[0023] As a preferred solution of the design and synthesis method of the semiconductor cluster-based photoresist according to the present application, wherein: the synthesis method of the ZnSe cluster comprises:

[0024] Zinc acetate is reacted with selenourea in a mixed solution of octylamine and butylamine;

[0025] Tris(octyl) phosphine and ethane-1,2-diyl bis(4-azido-2,3,5,6-tetrafluorobenzoate) are added to terminate the reaction;

[0026] The ZnSe cluster is obtained by centrifugation and solvent purification, and its characteristic absorption peak is located at 289 nm.

[0027] As a preferred solution of the design and synthesis method of the semiconductor cluster-based photoresist according to the present application, wherein: the synthesis method of the ZnS cluster comprises:

[0028] Zinc acetate is reacted with sulfur in octylamine;

[0029] The reaction is terminated by adding trioctylphosphine and ethane-1, 2-diyl bis(4-azido-2, 3, 5, 6-tetrafluorobenzoate);

[0030] The ZnS clusters are obtained by centrifugation and solvent purification, and have a characteristic absorption peak at 265 nm.

[0031] As a preferred scheme of the design and synthesis method of the semiconductor cluster-based photoresist according to the present application, the synthesis method of the InAs cluster comprises:

[0032] Indium chloride and zinc iodide are reacted with tris(dimethylamino)arsenic in oleylamine;

[0033] The reaction is terminated by adding ethane-1, 2-diyl bis(4-azido-2, 3, 5, 6-tetrafluorobenzoate);

[0034] The InAs clusters are obtained by centrifugation and solvent purification, and have a characteristic absorption peak at 501 nm.

[0035] As a preferred scheme of the design and synthesis method of the semiconductor cluster-based photoresist according to the present application, the solid content of the photoresist solution is 15-20 mg / mL, and the coating method is spin coating, and the spin coating parameters comprise: a final rotation speed of 3000±50 rpm, an angular acceleration of 1500 rpm / s, and a duration of 40±0.5 s. 2

[0036] As a preferred scheme of the design and synthesis method of the semiconductor cluster-based photoresist according to the present application, the ultraviolet light exposure adopts a 254 nm mercury lamp, the power density is 15 mW / cm2, and the light dose is 800±20 mJ / cm 2 ; the electron beam exposure parameters are a voltage of 30 kV, a beam current value of 0.45 nA, and an exposure dose of 200-1200 μC / cm 2 .

[0037] As a preferred scheme of the design and synthesis method of the semiconductor cluster-based photoresist according to the present application, the development process comprises:

[0038] Pulse solvent flushing is performed at a rotation speed of 4000±100 rpm using n-hexane, cyclohexane, octylamine, or toluene;

[0039] The spraying amount is 2.5±0.3 mL, and the spraying rate is 1.25 mL / s;

[0040] The selective peeling of the unexposed area is realized by centrifugal force.

[0041] ​As a preferred scheme of the design and synthesis method of the semiconductor cluster-based photoresist according to the present application, the linewidth of the patterned structure is micrometer level, and the thin film structure after patterning is complete without bubbles or cracks.

[0042] The present application has the following advantages: by using a semiconductor cluster with a clear structure as a photosensitive unit, the integration of photoetching function and material function is realized, without the need for additional photosensitizers or complex ligand modification, simplifying the synthesis path and significantly improving the material purity, the prepared cluster photoresist can be directly patterned under ultraviolet or electron beam exposure, avoiding the problems of poor thermal stability, residual impurities of traditional organic photoresist and structural defects caused by ligand decomposition of nanocrystal photoresist, obtaining a micrometer-level patterned structure with high resolution, high fidelity and excellent thin film integrity, which can meet the process requirements of high precision and high stability for semiconductor manufacturing. BRIEF DESCRIPTION OF DRAWINGS

[0043] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0044] Figure 1 Flowchart of the design and synthesis method of the semiconductor cluster-based photoresist in Example 1.

[0045] Figure 2 Comparison diagram of different photoetching and developing procedures in Example 1.

[0046] Figure 3 Sample diagram of the semiconductor cluster photoresist dispersion liquid in Example 1.

[0047] Figure 4 UV characteristic absorption spectrum of the semiconductor cluster photoresist in Example 1.

[0048] Figure 5 Patterning diagram of the semiconductor cluster photoresist in Example 1.

[0049] Figure 6 Patterning diagram of the Cd-based semiconductor cluster photoresist in Example 1.

[0050] Figure 7 Patterning diagram of the InP semiconductor cluster photoresist after electron beam exposure in Example 1. DETAILED DESCRIPTION

[0051] In order to make the above objectives, characteristics and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below with reference to the accompanying drawings.

[0052] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. However, the present application can be practiced in other ways that are not exactly as described in this description. It is understood that variations can be made in view of what is described and understood that it can be done without departing from the scope of the present application. Therefore, the present application is not limited by the specific embodiments disclosed below.

[0053] Secondly, the "one embodiment" or "embodiment" referred to herein means that the specific features, structures or characteristics can be included in at least one implementation of the present application. "In one embodiment" appearing in different places in this specification does not mean the same embodiment, nor does it mean an embodiment that is separate or alternative to other embodiments.

[0054] Embodiment, refer to Figures 1-7 For the embodiment of the present application, the embodiment provides a design and synthesis method based on semiconductor cluster photoresist, comprising the following steps:

[0055] S1, synthesis of semiconductor cluster photoresist material;

[0056] Further, the synthesis method comprises the following specific steps:

[0057] Preparation of precursor: for InP cluster, take 934 mg of indium acetate and 2.65 g of myristic acid into a 100 mL three-necked flask, vacuum degassing at 120℃ for 24 hours to remove acetic acid, then add 20 mL of super dry toluene; for ZnSe cluster, dissolve 27 mg of zinc acetate dihydrate and 24.6 mg of selenourea in 3 mL of mixed solvent of octylamine and butylamine; for ZnS cluster, dissolve 45 mg of Zn(OAc)2·2H2O in 6 mL of octylamine, and then add 4 mg of 1 mL octylamine solution of sulfur sheet; for InAs cluster, dissolve 74.2 mg of indium chloride and 702 mg of zinc iodide in 5 mL of oleylamine, and heat to 200℃ to completely dissolve the precursor;

[0058] Reaction: under the protection of inert gas, 465 μL of 10 mL toluene solution of tris (trimethylsilyl) phosphine is injected into the precursor solution at 110℃ for InP cluster, and the reaction is carried out for 30 minutes; ZnSe cluster is reacted at 70℃ for 12 hours; ZnS cluster is reacted at 80℃ for more than 15 hours; for InAs cluster, 0.114 mL of 0.5 mL oleylamine solution of tris (dimethylamino) arsenic is first injected, stirred at room temperature for 30 minutes, then 0.338 mL of tris (dimethylamino) phosphine solution is injected, and the reaction is carried out at 140℃ for 30 minutes;

[0059] Termination and purification: all reactions need to add 10 mg of ethane-1, 2-diyl bis (4-azido-2, 3, 5, 6-tetrafluorobenzoate) to terminate the reaction, InP cluster adopts 5000 rpm centrifugation for 3 minutes, the supernatant is precipitated by adding 30 mL of acetonitrile, and the operation is repeated 3 times; ZnSe cluster adopts 8000 rpm centrifugation for 30 seconds, amine / cyclohexane mixed solution purification 1-2 times; ZnS cluster 8000 rpm centrifugation for 30 seconds, octylamine purification; InAs cluster is purified by toluene after centrifugation;

[0060] Characterization: the characteristic absorption peaks of InP cluster are confirmed by ultraviolet-visible absorption spectrum, 398 nm for ZnSe cluster, 289 nm for ZnS cluster, 265 nm for InAs cluster, 501 nm for CdSe cluster, 324 nm for CdS cluster, and 440 nm for CdTe cluster;

[0061] The semiconductor cluster is selected from at least one of InP, ZnSe, ZnS, InAs, ZnTe, CdSe, CdS or CdTe;

[0062] It should be noted that by precisely controlling the precursor ratio, reaction temperature and time and other parameters, semiconductor clusters with uniform size and clear structure can be obtained, and the molecular level dissolution characteristics avoid the need for surface modification of traditional nanomaterials, and the precise control of characteristic absorption peaks ensures the consistency of the response of photoresist at a specific wavelength, laying a material foundation for subsequent patterning process.

[0063] S2, dissolving the semiconductor cluster material in an organic solvent to form a photoresist solution;

[0064] Further, substrate treatment: a silicon wafer with a size of 10x10x0.65mm is used as the substrate, the thickness tolerance is controlled within ±5μm, and the surface is treated by oxygen plasma for 10 minutes before use to improve the surface hydrophilicity;

[0065] Solution preparation: the purified semiconductor clusters are dissolved in the corresponding organic solvent at a solid content of 15-20mg / mL, InP cluster uses toluene, ZnSe cluster uses cyclohexane, ZnS cluster uses octylamine, InAs cluster uses toluene, CdSe cluster uses n-hexane, and the preparation process is completed in a nitrogen glove box;

[0066] Solution filtration: the prepared photoresist solution is filtered by using a 0.22μm polytetrafluoroethylene filter membrane to remove possible trace insoluble substances

[0067] It should be noted that the solution preparation process ensures the stability of the photoresist solution and the film forming quality by optimizing the solvent selection and solid content control, the oxygen plasma treatment significantly improves the substrate wettability, and the strict filtration procedure eliminates the particle contaminants that may affect the pattern accuracy, which together ensures the repeatability and reliability of the subsequent process.

[0068] S3, coating the photoresist solution on the substrate to form a homogeneous thin film;

[0069] Further, the coating process specifically includes:

[0070] Environmental control: all operations are completed in a yellow light room environment (wavelength range 580-600 nm), the environmental temperature is controlled at 22±1℃, and the relative humidity is maintained at 40±5%;

[0071] Dispensing process: using a micro dispensing system to accurately coat 10±1μL cluster solution on the surface of the substrate, the dispensing height is controlled at 1.0±0.1mm, and the dispensing speed is 0.5μL / s;

[0072] Spin coating parameters: using gradient spin coating process, the initial stage is accelerated at 1500r / min to 3000±50r / min final speed, maintaining 40±0.5s, and the acceleration curve adopts S-shaped gradual mode;

[0073] Film thickness control: real-time monitoring of film thickness by ellipsometer to ensure that the thin film thickness uniformity error is within ±3%;

[0074] It should be noted that the coating process realizes the sub-micron film thickness uniformity by accurately controlling the environmental parameters and spin coating dynamics, the S-shaped acceleration curve effectively reduces the edge accumulation effect in the spin coating process, and the real-time film thickness monitoring provides closed-loop control for process stability, which significantly improves the quality and consistency of the thin film.

[0075] S4, selective exposure of the thin film by ultraviolet light or electron beam to realize patterning;

[0076] Further, the exposure process specifically includes:

[0077] Ultraviolet exposure:

[0078] Using contact exposure mode, using quartz mask, applying a constant pressure clamping force of 3.2±0.5N through a precision pressure clamp to ensure that the gap between the mask and the film surface is <5μm;

[0079] The exposure light source is a 254nm mercury lamp with a power density of 15mW / cm 2 , a half peak width of 8nm, and a light dose controlled at 800±20mJ / cm2;

[0080] The exposure area temperature is maintained at 23±0.5°C by a thermostatic cooling system;

[0081] Electron beam exposure:

[0082] A 30kV accelerating voltage is used, the beam current value is 0.45nA, and the beam spot diameter is about 10nm;

[0083] The exposure dose gradient is set to 200-1200μC / cm 2 , and is automatically adjusted according to the pattern feature size;

[0084] A multi-layer scanning strategy is used, and the interval time between each layer scanning is ≥30s to reduce the heat accumulation effect;

[0085] It should be noted that the exposure process optimizes the exposure parameters and heat management strategy, which not only ensures sufficient photochemical reaction efficiency, but also avoids material degradation caused by overheating. The multi-layer scanning strategy effectively suppresses the proximity effect in electron beam exposure, and the pattern edge definition is improved by more than 30%, which provides a guarantee for high-precision patterning.

[0086] S5, removing the material in the unexposed area through a developing process to obtain a patterned structure;

[0087] Further, the developing process specifically includes:

[0088] Developing equipment: a customized centrifugal developing system is used, equipped with a precision solvent spraying device;

[0089] Developing procedure;

[0090] Initial stage: at a rotation speed of 4000±100rpm, pulse solvent spraying is used, the spraying amount is 2.5±0.3mL, the spraying rate is 1.25mL / s, and the duration is 2.0±0.1s;

[0091] Second stage: natural volatilization drying for 15±3s, and the environmental temperature is controlled at 25±1°C;

[0092] Solvent selection: according to the type of cluster, the developing solvent is matched, InP cluster uses n-hexane, ZnSe cluster uses cyclohexane, ZnS cluster uses octylamine, and InAs cluster uses toluene;

[0093] Quality control: the patterned structure is checked by an optical microscope (100x) to ensure that the line width reaches the micron level (1-5μm), the thin film is free of defects such as bubbles and cracks, and the residue removal rate is >99.5%;

[0094] It should be noted that the developing process realizes efficient removal of unexposed area material through innovative centrifugal auxiliary pulse jet technology, precise matching of solvent selectivity and cluster characteristics avoids over-etching, and a multi-parameter quality control system ensures the integrity of the patterned structure, which makes the yield of the process more than 15% higher than that of the traditional method.

[0095] In summary, by using a semiconductor cluster with a clear structure as a photosensitive unit, the present application realizes the integrated design of photoetching function and material function, without the need for additional photosensitizers or complex ligand modification, simplifying the synthesis path and significantly improving the material purity. The prepared cluster photoresist can be directly patterned under ultraviolet or electron beam exposure, avoiding the problems of poor thermal stability, residual impurities of traditional organic photoresist, and structural defects caused by ligand decomposition of nanocrystal photoresist. The obtained micron-scale patterned structure has high resolution, high fidelity and excellent film integrity, which can meet the process requirements of high precision and high stability for semiconductor manufacturing.

[0096] It should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit it. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the present application, which should be covered by the scope of the claims of the present application.

Claims

1. A method for designing and synthesizing semiconductor cluster photoresist, characterized in that: The application relates to a synthetic semiconductor cluster photoresist material, a preparation method of the semiconductor cluster photoresist material and a semiconductor cluster photoresist material. The semiconductor cluster material is dissolved in an organic solvent to form a photoresist solution; The photoresist solution is coated on a substrate to form a homogeneous thin film; The thin film is selectively exposed to ultraviolet light or an electron beam to realize patterning; The material in the unexposed area is removed through a developing process to obtain a patterned structure. The semiconductor cluster is selected from at least one of InP, ZnSe, ZnS, InAs, ZnTe, CdSe, CdS or CdTe. The synthesis method of the semiconductor cluster comprises the following steps:

2. The design and synthesis method based on semiconductor cluster photoresist according to claim 1, wherein: A metal precursor and an anion precursor are prepared; The metal precursor and the anion precursor are reacted in an organic solvent under the protection of an inert gas to generate semiconductor clusters; The semiconductor clusters are separated through centrifugation and a purification step; The characteristic absorption peak of the semiconductor clusters is confirmed through ultraviolet-visible absorption spectrum characterization. The synthesis method of the InP cluster comprises the following steps:

3. The design and synthesis method based on semiconductor cluster photoresist according to claim 2, wherein: An indium myristate precursor is reacted with tris(trimethylsilyl) phosphine in toluene; Ethane-1,2-diyl bis (4-azido-2,3,5,6-tetrafluorobenzoate) is added as an auxiliary dispersant; InP clusters are obtained through centrifugation and solvent purification, and the characteristic absorption peak is located at 398 nm. The synthesis method of the ZnSe cluster comprises the following steps:

4. The design and synthesis method based on semiconductor cluster photoresist according to claim 3, wherein: Zinc acetate is reacted with selenourea in a mixed solution of octylamine and butylamine; Tris(octyl) phosphine and ethane-1,2-diyl bis (4-azido-2,3,5,6-tetrafluorobenzoate) are added to terminate the reaction; ZnSe clusters are obtained through centrifugation and solvent purification, and the characteristic absorption peak is located at 289 nm. The synthesis method of the ZnS cluster comprises the following steps:

5. The design and synthesis method based on semiconductor cluster photoresist according to claim 4, wherein: Zinc acetate is reacted with sulfur in octylamine; Tris(octyl) phosphine and ethane-1,2-diyl bis (4-azido-2,3,5,6-tetrafluorobenzoate) are added to terminate the reaction; ZnS clusters are obtained through centrifugation and solvent purification, and the characteristic absorption peak is located at 265 nm. The synthesis method of the InAs cluster comprises the following steps:

6. The design and synthesis method based on semiconductor cluster photoresist according to claim 5, wherein: Indium chloride and zinc iodide are reacted with tris(dimethylamino) arsenic in oleylamine; Ethane-1,2-diyl bis (4-azido-2,3,5,6-tetrafluorobenzoate) is added to terminate the reaction; InAs clusters are obtained through centrifugation and solvent purification, and the characteristic absorption peak is located at 501 nm. The developing process comprises the following steps:

7. The method of claim 6, wherein the semiconductor cluster photoresist based design and synthesis is characterized by: The solid content of the photoresist solution is 15-20 mg / mL, the coating method is spin coating, and the spin coating parameters include: a final rotation speed of 3000±50 rpm, an angular acceleration of 1500 rpm / s, and a duration of 40±0.5 s. 2 , a duration of 40±0.5 s.

8. The method of design and synthesis of semiconductor cluster based photoresist according to claim 7, wherein: The UV exposure uses a 254 nm mercury lamp with a power density of 15 mW / cm2and a light dose of 800 ± 20 mJ / cm2 2 ; the electron beam exposure parameters are a voltage of 30 kV, a beam value of 0.45 nA, and an exposure dose of 200-1200 μC / cm 2 .

9. The method of claim 8, wherein the semiconductor cluster photoresist based design and synthesis is characterized by: Pulse solvent flushing is carried out at a rotating speed of 4000+ / -100 rpm by using n-hexane, cyclohexane, octylamine or toluene; The spraying amount is 2.5+ / -0.3 mL, and the spraying rate is 1.25 mL / s; The selective stripping of the unexposed area is realized through centrifugal force. The line width of the patterned structure is micron level, and the patterned thin film structure is complete, without bubbles or cracks.

10. The method of claim 9, wherein the semiconductor cluster photoresist based design and synthesis is characterized by: ​

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