阅读说明：本技术 一种具有微纳结构的氧化锌薄膜材料的制备方法 (Preparation method of zinc oxide film material with micro-nano structure ) 是由 陈战东 于 2019-11-22 设计创作，主要内容包括：本发明涉及半导体材料制备技术领域,具体为一种具有微纳结构的氧化锌薄膜材料的制备方法,包括镀膜、预烘、匀胶、前烘、曝光、显影与清洗、后烘、腐蚀、高温退火氧化共九个步骤。本发明通过合理运用光刻技术和真空蒸镀技术,在硅片表面先制作出圆柱状锌薄膜阵列,然后在自然空气环境下,将硅片放入高温退火炉中,再向高温炉内的石英管腔体注入空气对锌薄膜进行高温氧化,从而制备出氧化锌薄膜材料。本方法与现有技术相比具有成本低廉,制备过程容易控制等优点。(The invention relates to the technical field of semiconductor material preparation, in particular to a preparation method of a zinc oxide film material with a micro-nano structure, which comprises nine steps of film coating, pre-drying, glue homogenizing, pre-drying, exposure, development and cleaning, post-drying, corrosion and high-temperature annealing oxidation. According to the invention, by reasonably applying the photoetching technology and the vacuum evaporation technology, a cylindrical zinc film array is firstly manufactured on the surface of a silicon wafer, then the silicon wafer is placed in a high-temperature annealing furnace in a natural air environment, and then air is injected into a quartz tube cavity in the high-temperature annealing furnace to carry out high-temperature oxidation on a zinc film, so that the zinc oxide film material is prepared. Compared with the prior art, the method has the advantages of low cost, easy control of the preparation process and the like.)

1. A preparation method of a zinc oxide film material with a micro-nano structure is characterized by comprising the following steps:

step (1), coating: plating a zinc film on the silicon wafer;

pre-baking: putting a silicon chip coated with a zinc film into a ceramic crucible, and then putting the silicon chip into the ceramic crucible

Baking for the first time in the baking oven;

homogenizing glue in the step (3): taking the silicon wafer out of the oven, placing the silicon wafer in a normal temperature environment, and after the silicon wafer is naturally cooled, placing the silicon wafer into a sucker of a spin coater for spin coating;

pre-baking in step (4): placing the silicon wafer coated with the photoresist in a crucible, wrapping the crucible with tinfoil, and placing the crucible in an oven for secondary baking;

step (5), exposure: exposing and photoetching the silicon wafer subjected to prebaking by using a photoetching machine, namely, placing a mask plate right above the silicon wafer, and exposing the silicon wafer by aligning the center of an ultraviolet light source to the mask plate for 3-4 s;

and (6) developing and cleaning: immersing the exposed silicon wafer in a developing solution for 13s-17s, taking out the silicon wafer after the developing solution is fully developed, putting the silicon wafer into deionized water for cleaning for 20s-40s, and drying the deionized water on the surface of the silicon wafer by using nitrogen after cleaning is finished;

and (7) postbaking: placing the developed silicon wafer into an oven for third baking;

and (8) corrosion: immersing the silicon wafer into dilute hydrochloric acid for chemical corrosion for 30-50 s, after removing the zinc film outside the photoresist attachment area, washing the silicon wafer clean by deionized water, then washing the photoresist by acetone, and after removing the photoresist, washing the silicon wafer clean by deionized water;

step (9), high-temperature annealing oxidation: putting a corroded silicon wafer with a zinc film with a micro-nano structure into a high-temperature annealing furnace for oxidation, wherein the oxidation process comprises the following six stages:

the first stage, the temperature in the furnace is normal temperature, and the time is 30 min;

the second stage, the temperature in the furnace is 300 ℃, and the time is 20 min;

the third stage, the temperature in the furnace is 300 ℃, and the time is 10 min;

the fourth stage, the temperature in the furnace is 370-385 ℃, and the time is 500-700 min;

the fifth stage, the temperature in the furnace is 370-385 ℃, and the time is 40 min;

and in the sixth stage, the silicon wafer is taken out when the temperature in the furnace is reduced to room temperature, and the preparation of the zinc oxide film material with the micro-nano structure is completed.

2. The preparation method of the zinc oxide film material with the micro-nano structure according to claim 1, wherein the coating is a plasma sputtering coating, and the steps are as follows:

the first step is as follows: putting the silicon wafer into a beaker containing alcohol, then putting the beaker into an ultrasonic cleaning machine for cleaning for 5-15 min, clamping the silicon wafer out by using tweezers after cleaning, and drying the residual alcohol solution on the surface of the silicon wafer by using nitrogen;

the second step is that: clamping the cleaned silicon wafer on a substrate table of a plasma experimental instrument, adjusting the height of the substrate table to enable the distance between the substrate table and a zinc target to be 10-15 mm, and covering a cover of a vacuum chamber;

the third step: sequentially turning on a main power supply, cooling water, a vacuum pump and a resistance vacuum gauge button of the plasma experimental instrument, and then turning on a direct-current sputtering knob, wherein the sputtering air inlet knob must be kept in a closed state;

the fourth step: when the pressure of the vacuum chamber is reduced to 10-20 Pa, a switch knob of a working gas cylinder is unscrewed, a sputtering gas inlet knob is turned on, and the sputtering gas inlet knob and a direct current sputtering knob are adjusted to stabilize the pressure of the vacuum chamber at 15-20 Pa;

the fifth step: turning on a high-voltage power switch, rotating a high-voltage adjusting coarse adjustment knob, controlling the voltage between two electrodes of a vacuum chamber to be 700V-800V and the current to be 10mA-15mA, and plating a zinc film on a silicon wafer according to the direct-current sputtering principle for 20min-40 min;

and a sixth step: after the film coating is finished, firstly rotating a high-voltage adjusting coarse adjustment knob to adjust the voltage of the vacuum chamber to zero, then closing a high-voltage power switch, and then sequentially closing a sputtering air inlet knob, a direct-current sputtering knob, a resistance vacuum gauge, a vacuum pump, cooling water, a main power supply and a switch knob of a working gas cylinder;

the seventh step: and (4) loosening an air inlet knob of the vacuum chamber, slowly filling the air, taking down a cover of the vacuum chamber, taking out the silicon wafer subjected to film coating by using tweezers, and putting the silicon wafer into a sample box.

3. The preparation method of the zinc oxide film material with the micro-nano structure according to claim 1, which is characterized by comprising the following steps: the first baking temperature is 90-100 ℃ and the time is 15-30 min, the second baking temperature is 100 ℃ and the time is 4-6 min, and the third baking temperature is 100 ℃ and the time is 3-5 min.

4. The preparation method of the zinc oxide film material with the micro-nano structure according to claim 1, which is characterized by comprising the following steps: the spin coating refers to dripping photoresist into the center of the silicon wafer until the photoresist is fully distributed on the whole silicon wafer, pressing down a photoresist homogenizing switch of a photoresist homogenizer, homogenizing for 8s-10s under the condition of the rotating speed of 400r/min-500r/min, then increasing the rotating speed to 3500r/min-5000r/min, and continuing rotating for 25s-35s until the thickness of the photoresist is 3 mu m-5 mu m.

5. The preparation method of the zinc oxide film material with the micro-nano structure according to claim 4, which is characterized by comprising the following steps: the photoresist is RZJ-304 positive photoresist.

6. The preparation method of the zinc oxide film material with the micro-nano structure according to claim 1, which is characterized by comprising the following steps: the mask is square, a circular array is arranged in the middle of the mask, the circular array is composed of M rows and N columns of circles, wherein M is more than or equal to 2 and less than or equal to 100 and is an integer, N is more than or equal to 2 and less than or equal to 100 and is an integer, the diameter r1 of each circle is 1-10 mu M, and the transverse distance d between every two circles₁Is 1 μm to 10 μm, and the longitudinal distance d between every two circles₂Is 1 μm to 10 μm.

7. The preparation method of the zinc oxide film material with the micro-nano structure according to claim 1, which is characterized by comprising the following steps: the concentration ratio of the dilute hydrochloric acid is 1: 1000.

8. The preparation method of the zinc oxide film material with the micro-nano structure according to claim 2, which is characterized by comprising the following steps: the zinc thin filmThickness h of₁Is 5nm-20 nm.

9. The preparation method of the zinc oxide film material with the micro-nano structure according to claim 2, which is characterized by comprising the following steps: the working gas cylinder is an argon gas cylinder or an oxygen gas cylinder.

Technical Field

The invention relates to the technical field of semiconductor material preparation, in particular to a preparation method of a zinc oxide film material with a micro-nano structure.

Background

Zinc oxide is a direct wide-band gap semiconductor material, has excellent characteristics of piezoelectricity, photoelectricity, gas sensitivity, pressure sensitivity and the like, has wide application in transparent conductors, light-emitting elements, solar cell window materials, optical waveguides, monochromatic long-emission display devices and the like, and is considered to be a third-generation semiconductor material. Meanwhile, with the miniaturization and integration of semiconductor devices, nano zinc oxide materials with structures such as zinc oxide films, zinc oxide quantum dots, zinc oxide nano particles and the like become important points for the research in the field of semiconductor materials. The preparation method of the zinc oxide nano material commonly used at present mainly comprises the following steps: molecular Beam Epitaxy (MBE), Ultrasonic Spray Pyrolysis (USP), magnetron sputtering, chemical vapor deposition (MOCVD), sol-gel (sol-gel), etc., all of which have disadvantages such as high cost and complicated control, and thus it is finally difficult to mass-produce such nano zinc oxide materials.

Disclosure of Invention

Aiming at the problems, according to the preparation method of the zinc oxide film material with the micro-nano structure, disclosed by the invention, by reasonably utilizing a photoetching technology and a vacuum evaporation technology, a cylindrical zinc film array is firstly prepared on the surface of a silicon wafer, then the silicon wafer is placed into a high-temperature annealing furnace in a natural air environment, and then air is injected into a quartz tube cavity in the high-temperature annealing furnace to carry out high-temperature oxidation on the zinc film, so that the zinc oxide film material is finally prepared. The invention has the advantages of low cost, easy control of the preparation process and the like, and effectively solves the problems.

The technical scheme adopted by the invention is as follows:

a preparation method of a zinc oxide film material with a micro-nano structure is characterized by comprising the following steps:

step (1), coating: plating a zinc film on the silicon wafer;

pre-baking: putting a silicon chip coated with a zinc film into a ceramic crucible, and then putting the silicon chip into the ceramic crucible

Baking for the first time in the baking oven;

homogenizing glue in the step (3): taking the silicon wafer out of the oven, placing the silicon wafer in a normal temperature environment, and after the silicon wafer is naturally cooled, placing the silicon wafer into a sucker of a spin coater for spin coating;

pre-baking in step (4): placing the silicon wafer coated with the photoresist in a crucible, wrapping the crucible with tinfoil, and placing the crucible in an oven for secondary baking;

step (5), exposure: exposing and photoetching the silicon wafer subjected to prebaking by using a photoetching machine, namely, placing a mask plate right above the silicon wafer, and exposing the silicon wafer by aligning the center of an ultraviolet light source to the mask plate for 3-4 s;

and (6) developing and cleaning: immersing the exposed silicon wafer in a developing solution for 13s-17s, taking out the silicon wafer after the developing solution is fully developed, putting the silicon wafer into deionized water for cleaning for 20s-40s, and drying the deionized water on the surface of the silicon wafer by using nitrogen after cleaning is finished;

and (7) postbaking: placing the developed silicon wafer into an oven for third baking;

the post-baking is to improve the adhesive force of the photoresist to the silicon wafer, and simultaneously improve the corrosion resistance of the photoresist film, so that the good performance can be kept when the chemical corrosion is carried out in the later step.

And (8) corrosion: immersing the silicon wafer into dilute hydrochloric acid for chemical corrosion for 30-50 s, after removing the zinc film outside the photoresist attachment area, washing the silicon wafer clean by deionized water, then washing the photoresist by acetone, and after removing the photoresist, washing the silicon wafer clean by deionized water;

step (9), high-temperature annealing oxidation: putting a corroded silicon wafer with a zinc film with a micro-nano structure into a high-temperature annealing furnace for oxidation, wherein the oxidation process comprises the following six stages:

the first stage, the temperature in the furnace is normal temperature, and the time is 30 min;

the second stage, the temperature in the furnace is 300 ℃, and the time is 20 min;

the third stage, the temperature in the furnace is 300 ℃, and the time is 10 min;

the fourth stage, the temperature in the furnace is 370-385 ℃, and the time is 500-700 min;

the fifth stage, the temperature in the furnace is 370-385 ℃, and the time is 40 min;

and in the sixth stage, the silicon wafer is taken out when the temperature in the furnace is reduced to room temperature, and the preparation of the zinc oxide film material with the micro-nano structure is completed.

Further, the coating adopts plasma sputtering coating, and the steps are as follows:

the first step is as follows: putting the silicon wafer into a beaker containing alcohol, then putting the beaker into an ultrasonic cleaning machine for cleaning for 5-15 min, clamping the silicon wafer out by using tweezers after cleaning, and drying the residual alcohol solution on the surface of the silicon wafer by using nitrogen;

the second step is that: clamping the cleaned silicon wafer on a substrate table of a plasma experimental instrument, adjusting the height of the substrate table to enable the distance between the substrate table and a zinc target to be 10-15 mm, and covering a cover of a vacuum chamber;

the third step: sequentially turning on a main power supply, cooling water, a vacuum pump and a resistance vacuum gauge button of the plasma experimental instrument, and then turning on a direct-current sputtering knob, wherein the sputtering air inlet knob must be kept in a closed state;

the fourth step: when the pressure of the vacuum chamber is reduced to 10-20 Pa, a switch knob of a working gas cylinder is unscrewed, a sputtering gas inlet knob is turned on, and the sputtering gas inlet knob and a direct current sputtering knob are adjusted to stabilize the pressure of the vacuum chamber at 15-20 Pa;

the fifth step: turning on a high-voltage power switch, rotating a high-voltage adjusting coarse adjustment knob, controlling the voltage between two electrodes of a vacuum chamber to be 700V-800V and the current to be 10mA-15mA, and plating a zinc film on a silicon wafer according to the direct-current sputtering principle for 20min-40 min;

the thickness of the plated zinc film directly determines the thickness of the micro-nano structure of the zinc oxide film material.

And a sixth step: after the film coating is finished, firstly rotating a high-voltage adjusting coarse adjustment knob to adjust the voltage of the vacuum chamber to zero, then closing a high-voltage power switch, and then sequentially closing a sputtering air inlet knob, a direct-current sputtering knob, a resistance vacuum gauge, a vacuum pump, cooling water, a main power supply and a switch knob of a working gas cylinder;

the seventh step: and (4) loosening an air inlet knob of the vacuum chamber, slowly filling the air, taking down a cover of the vacuum chamber, taking out the silicon wafer subjected to film coating by using tweezers, and putting the silicon wafer into a sample box.

Further, the first baking temperature is 90-100 ℃, the time is 15-30 min, and the second baking temperature is

The secondary baking temperature is 100 deg.C for 4-6 min, and the third baking temperature is 100 deg.C for 3-5 min.

Further, the spin coating refers to dripping photoresist into the center of the silicon wafer until the photoresist is fully distributed on the whole silicon wafer, pressing a photoresist homogenizing switch of a photoresist homogenizer, homogenizing for 8s-10s under the condition of the rotating speed of 400r/min-500r/min, then increasing the rotating speed to 3500r/min-5000r/min, and continuing rotating for 25s-35s until the thickness of the photoresist is 3 μm-5 μm.

Further, the photoresist is RZJ-304 positive photoresist.

Go toThe mask is square, a circular array is arranged in the middle of the mask, the circular array is composed of M rows and N columns of circles, wherein M is more than or equal to 2 and less than or equal to 100 and is an integer, N is more than or equal to 2 and less than or equal to 100 and is an integer, the diameter r1 of each circle is 1-10 mu M, and the transverse distance d between every two circles₁Is 1 μm to 10 μm, and the longitudinal distance d between every two circles₂Is 1 μm to 10 μm.

The number of circles of the mask circular array and the diameter thereof, and the transverse distance and the longitudinal distance between every two circles determine the micro-nano structure of the zinc oxide film material.

Further, the concentration ratio of the dilute hydrochloric acid is 1: 1000.

Further, the thickness h of the zinc film₁Is 5nm-20 nm.

Further, the working gas cylinder is an argon gas cylinder or an oxygen gas cylinder.

In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:

according to the preparation method of the zinc oxide film material with the micro-nano structure, a cylindrical zinc film array is firstly prepared on the surface of a silicon wafer by reasonably utilizing a photoetching technology and a vacuum evaporation technology, then the silicon wafer is placed into a high-temperature annealing furnace in a natural air environment, and then air is injected into a quartz tube cavity in the high-temperature annealing furnace to carry out high-temperature oxidation on the zinc film, so that the zinc oxide film material is prepared. Compared with the prior art, the method has the advantages of low cost, easy control of the preparation process and the like, thereby having the prospect of mass production and large-scale popularization and application.

Drawings

In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings required in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some examples of the present invention, and it is also possible for a person skilled in the art to obtain other drawings based on these drawings without inventive step.

FIG. 1 is a work flow diagram of a method of preparation;

FIG. 2 is a top view of a reticle;

FIG. 3 is a side view of a cylindrical array of zinc films;

FIG. 4 is a top view of a cylindrical array of zinc films;

FIG. 5 is a schematic diagram of a high temperature oxidation of a zinc thin film material;

figure 6 side view of finished zinc oxide film material.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the examples of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.