Film evaporation method
阅读说明:本技术 薄膜蒸镀方法 (Film evaporation method ) 是由 刘宇 于 2018-07-04 设计创作,主要内容包括:本发明提供一种薄膜蒸镀方法,包括以下步骤:S1:在薄膜蒸镀装置中,将多个不同组分的靶材沿第一方向设置;S2:使衬底与所述靶材在所述第一方向上发生相对运动的同时使所述靶材蒸发,在所述衬底上沉积形成薄膜。(The invention provides a film evaporation method, which comprises the following steps: s1: in a film evaporation device, a plurality of targets with different components are arranged along a first direction; s2: and evaporating the target while the substrate and the target move relatively in the first direction, and depositing to form a film on the substrate.)
1. A film evaporation method is characterized by comprising the following steps:
s1: in a film evaporation device, a plurality of targets with different components are arranged along a first direction;
s2: and evaporating the target while the substrate and the target move relatively in the first direction, and depositing to form a film on the substrate.
2. A thin film evaporation method according to claim 1, wherein the plurality of targets of different compositions includes a first alloy target, a second alloy target, and a third alloy target arranged in this order along the first direction,
the composition of the first alloy target material comprises Cu(0.01~1.0)In(0.01~1.0)Ga(0.01~1.0)Se(0.01~3.0);
The composition of the second alloy target material comprises Cu(0.01~2.0)In(0~1.0)Ga(0~1.0)Se(0.01~3.0);
The composition of the third alloy target material comprises Cu(0.01~2.0)In(0.01~1.5)Ga(0.01~1.0)Se(0.01~3.0)。
3. The method of claim 2, wherein the first alloy target, the second alloy target and the third alloy target are sequentially and respectively made of Cu0.1In0.3Ga1.0Se0.5、Cu2.0Se0.5、Cu0.1In0.5Ga1.0Se0.5。
4. A method as recited in claim 1, wherein said plurality of different composition targets further comprises a buffer layer target disposed at a distal end of said plurality of different composition targets along said first direction.
5. The method of claim 4, wherein the buffer layer target is GdS target.
6. The method as claimed in claim 4, further comprising feeding H into said thin film deposition apparatus while performing said step S22And S, gas, wherein the buffer layer target is a Cd target.
7. The method of claim 1, wherein the evaporation temperature of the target is 500-1100 ℃.
8. The method according to claim 1, wherein step S2 comprises heating the plurality of compositionally different targets uniformly to a same temperature.
9. A method according to claim 1, wherein each target has a length in the first direction of 1m-5m, and the relative motion speed of the target and the substrate is less than or equal to 3 m/min.
10. The method of claim 9, wherein the target is spaced from the substrate by a distance of 5mm to 50 mm.
11. A method as claimed in claim 1, wherein step S2 comprises receiving the substrate by a substrate carrier and driving the substrate to move along a first direction.
12. The method according to claim 11, wherein the step S1 includes fixing the targets with different compositions on a same target fixing device along the first direction, the target fixing device having a cylindrical sidewall for fixing the targets, the first direction being a circumferential direction of the cylindrical sidewall, and the substrate supporting device being sleeved outside the target fixing device and having an arc-shaped supporting surface coaxially disposed with the cylindrical sidewall for supporting the substrate.
13. The method according to claim 11, wherein step S1 includes fixing the targets with different compositions along the first direction on a same target fixing device, wherein the target fixing device is flat, and the substrate holder has a flat carrying surface for carrying the substrate.
Technical Field
The invention relates to the field of film preparation, in particular to a film evaporation method.
Background
Copper indium selenide (CuInSe)2CIS for short or CuInGaSe (CuIn)xGa1-xSe2CIGS for short) thin-film solar cells are one of the research hotspots of solar cell materials in various countries because the thin-film solar cells have high photoelectric conversion efficiency, relatively low manufacturing cost, stable performance, no light-induced decay and lower price than the traditional crystalline silicon cells.
The CIGS thin-film solar cell mainly comprises a glass substrate, a molybdenum (Mo) back electrode, a CIGS absorption layer, a buffer layer, a window layer, an antireflection layer and an aluminum electrode, wherein the CIGS absorption layer is a core material in the solar cell, and one of key technologies for preparing the efficient CIGS thin-film solar cell is to obtain a high-quality absorption layer, namely a CIGS thin film. The preparation methods of the CIGS thin film are various, and the main preparation methods can be roughly classified into a vacuum preparation technology and a non-vacuum preparation technology. The vacuum preparation process mainly comprises a multi-source co-evaporation technology, a sputtering technology, a molecular beam epitaxy technology, a chemical vapor deposition technology and the like; and non-vacuum fabrication techniques include electrodeposition, spin coating, and screen printing. Although the preparation methods of the CIGS thin film are various, only the multisource co-evaporation technology and the selenization after sputtering are used for preparing the CIGS solar cell with high efficiency. Both evaporation and sputtering methods of preparation are used in japan, usa and germany, both in the laboratory and in the production line.
When a small-area CIGS thin film solar cell is prepared in a laboratory, the CIGS thin film deposited by the co-evaporation method has good quality and high cell efficiency, but the evaporation method cannot accurately control the element proportion, has poor repeatability and low material utilization rate, and is difficult to realize large-area uniform and stable film formation, so the application of the CIGS thin film solar cell in large-scale industrial production is limited.
Chinese patent application 200910089397.5 generated plasma around the selenium evaporation crucible in a direct current manner to ionize the selenium vapor, and the copper indium gallium was evaporated separately to deposit the CIGS film. The preparation method realizes the preparation of the CIGS thin film with large area by adopting a multi-element co-evaporation method. However, in this way, the copper indium gallium pre-fabricated layer is taken out of the vacuum chamber at risk of oxidation of the copper indium gallium, and in particular, the complete CIGS absorber layer deposited on the substrate must be taken out of the vacuum chamber several times at risk of oxidation of the respective evaporated layers. Moreover, this risk is not easily ruled out. Therefore, it is necessary to provide an evaporation method capable of effectively preventing the CIGS thin film from being oxidized during the evaporation process.
Disclosure of Invention
In view of the above, it is necessary to provide a thin film evaporation method for solving the problem that the CIGS thin film is easily oxidized during the evaporation process.
A film evaporation method comprises the following steps:
s1: in a film evaporation device, a plurality of targets with different components are arranged along a first direction;
s2: and evaporating the target while the substrate and the target move relatively in the first direction, and depositing to form a film on the substrate.
In one embodiment, the plurality of targets of different compositions includes a first alloy target, a second alloy target and a third alloy target arranged in sequence along the first direction,
the composition of the first alloy target material comprises Cu(0.01~1.0)In(0.01~1.0)Ga(0.01~1.0)Se(0.01~3.0);
The composition of the second alloy target material comprises Cu(0.01~2.0)In(0~1.0)Ga(0~1.0)Se(0.01~3.0);
The composition of the third alloy target material comprises Cu(0.01~2.0)In(0.01~1.5)Ga(0.01~1.0)Se(0.01~3.0)。
In one embodiment, the first alloy target, the second alloy target and the third alloy target respectively have the compositions of Cu in sequence0.1In0.3Ga1.0Se0.5、Cu2.0Se0.5、Cu0.1In0.5Ga1.0Se0.5。
In one embodiment, the plurality of different composition targets further includes a buffer layer target disposed at an end of the plurality of different composition targets along the first direction.
In one embodiment, the buffer layer target is an GdS target.
In one embodiment, the method further includes feeding H into the thin film evaporation apparatus while performing the step S22And S, gas, wherein the buffer layer target is a Cd target.
In one embodiment, the evaporation temperature of the target material is 500-1100 ℃.
In one embodiment, the step S2 includes heating the plurality of compositionally different targets to the same temperature.
In one embodiment, each target has a length in the first direction of 1m to 5m, and the relative motion of the target and the substrate has a velocity of less than or equal to 3 m/min.
In one embodiment, the target is spaced from the substrate by 5mm to 50 mm.
In one embodiment, the step S2 includes receiving the substrate by a substrate carrier and moving the substrate along a first direction.
In one embodiment, the step S1 includes fixing the targets with different compositions on the same target fixing device along the first direction, where the target fixing device has a cylindrical sidewall for fixing the targets, the first direction is a circumferential direction of the cylindrical sidewall, and the substrate supporting device is sleeved outside the target fixing device and has an arc-shaped supporting surface coaxially disposed with the cylindrical sidewall for supporting the substrate.
In one embodiment, the step S1 includes fixedly disposing the plurality of targets with different compositions on the same target fixing device along the first direction, where the target fixing device is a flat plate, and the substrate supporting device has a flat supporting surface for supporting the substrate.
According to the film evaporation method, the plurality of targets with different components are arranged along the first direction, and then the substrate and the targets are relatively displaced in the first direction, so that the materials of the plurality of targets are sequentially evaporated on the substrate to directly form the plurality of coating layers.
Drawings
FIG. 1 is a flow chart of an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a thin film deposition apparatus according to an embodiment of the present invention;
FIG. 3 is a schematic view of a heating device arrangement according to an embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a thin film deposition apparatus according to another embodiment of the present invention;
fig. 5 is a schematic structural diagram of an annular thin film evaporation apparatus according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the thin film deposition apparatus and the thin film deposition method of the present invention will be described in further detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only. The various objects of the drawings are drawn to scale for ease of illustration and not to scale for actual components.
Referring to fig. 1, an embodiment of the present invention further provides a thin film evaporation method, including the following steps:
s1: in a film evaporation device, a plurality of targets with different components are arranged along a first direction;
s2: and evaporating the target while the substrate and the target move relatively in the first direction, and depositing to form a film on the substrate.
According to the film evaporation method, the plurality of targets with different components are arranged along the first direction, and then the substrate and the targets are relatively displaced in the first direction, so that the materials of the plurality of targets are sequentially evaporated on the substrate to directly form the plurality of coating layers.
Referring to fig. 2, in a preferred embodiment, the
Target 302: cu(0.01~2.0)In(0~1.0)Ga(0~1.0)Se(0.01~3.0);
Target material 303: cu(0.01~2.0)In(0.01~1.5)Ga(0.01~1.0)Se(0.01~3.0)。
The CIGS target is used for preparing a CIGS thin film with a multilayer structure. Compared with the traditional solar cell with a single CIGS film layer, the solar cell with the CIGS film with the multilayer structure can have larger open-circuit voltage and short-circuit current, so that the photoelectric conversion efficiency of the CIGS film solar cell is improved to a great extent.
More preferably, the 3
target material 301: cu(0.01~0.5)In(0.01~0.5)Ga(0.5~1.0)Se(0.01~3.0);
Target 302: cu(1.0~2.0)In(0~0.5)Ga(0~0.5)Se(0.01~3.0);
Target material 303: cu(0.01~0.5)In(0.5~1.5)Ga(0.5~1.0)Se(0.01~3.0)。
The content and the distribution of Cu, Ga and In elements In the CIGS thin film are controlled by adjusting the content of Cu, Ga and In elements In each alloy target In the CIGS target, so that the energy band gap of a first thin film layer of the CIGS thin film evaporated by the CIGS target ranges from 1.3eV to 1.5eV, the energy band gap of a second thin film layer ranges from 0.9eV to 1.1eV, the energy band gap of a third thin film layer ranges from 1.1eV to 1.3eV, and the energy band gaps of three thin film layers stacked In the CIGS thin film prepared by the alloy material group are In double-band-gap gradient distribution In the thickness direction of the thin film. The open-circuit voltage and short-circuit current and conversion efficiency of a solar cell prepared by using the CIGS thin film are effectively improved.
In a preferred embodiment, the
In order to provide a CIGS thin film with a graded double band gap distribution, it is preferable that the
More preferably, the composition of the
In one embodiment, the
In another embodiment, the
In one embodiment, the alkali metal doping may be performed only on the
In a preferred embodiment, the purity of the
In order to vary the content of each element in the obtained CIGS thin film at different thickness positions of the CIGS thin film, and even separate at least three thin film layers with different components, the lengths of the
Preferably, the length of the
At the same temperature, the evaporation rates of the elements Cu, In, Ga and Se are not consistent, so that the partial pressures of the vapor formed In the evaporation chamber by the elements Cu, In, Ga and Se are not consistent, and therefore, the compositions of the finally formed first thin film layer, second thin film layer and third thin film layer are not completely consistent with the compositions of the
Referring to fig. 4, the
In one embodiment, in the thin film evaporation method, the length of each target is 1m-5m, and the relative movement speed of the target and a substrate to be evaporated is less than or equal to 3 m/min. More preferably, the relative motion between the target and the substrate is uniform, and of course, the relative motion may be non-uniform according to the consumption of the target or the actual demand of the substrate evaporation, and may be adjusted according to the actual process demand. The distance between the target and the substrate is 5mm-50mm, preferably 10mm-35 mm; more preferably, the distance is 15mm-25mm, and the arrangement of the distance ensures that components evaporated from the target material can be quickly deposited on the substrate, prevents the evaporation components of each target material from diffusing to other evaporation components of the target material and mixing, and ensures that the components of each coating layer are uniform and stable.
In one embodiment, step S2 includes receiving the substrate by a substrate carrier and moving the substrate in a first direction. Preferably, the substrate carrying device adsorbs the substrate by magnetic force or vacuum adsorption and drives the substrate to move along the first direction.
Preferably, the step S1 includes fixedly disposing the plurality of targets with different compositions on the same target fixing device along the first direction.
In a preferred embodiment, the target fixing device and the substrate carrying device are both flat, the substrate carrying device has a flat carrying surface for carrying the substrate, the target fixing device and the substrate carrying device are arranged in parallel, and the length directions of the target fixing device and the substrate carrying device are the same.
Preferably, the evaporation temperature of the target is 500 ℃ to 1100 ℃, more preferably 600 ℃ to 1000 ℃, and still more preferably 700 ℃ to 900 ℃, and in such a temperature range, the evaporation rate of the target is more stable, enabling the evaporation gas to be uniformly deposited on the substrate. In a preferred embodiment, the plurality of targets are heated to the same temperature, so that the evaporation rate of each target is uniform, which makes the deposition of the target composition on the substrate more uniform.
In another embodiment, the target fixing device has a cylindrical sidewall for fixing the target, the first direction is a circumferential direction of the cylindrical sidewall, the substrate bearing device is sleeved outside the target fixing device and has an arc-shaped bearing surface coaxially arranged with the cylindrical sidewall for bearing the substrate, and the target is fixed on a side of the target fixing device facing the substrate bearing device. The substrate moves from one end of the opening of the arc-shaped plate to the target direction, and moves out from the other end of the arc-shaped plate after circling for a circle. In this way, the technological process of film evaporation greatly reduces the floor area of the production equipment.
According to the film evaporation method, the plurality of targets with different components are arranged along the first direction, and then the substrate and the targets are relatively displaced in the first direction, so that the materials of the plurality of targets are sequentially evaporated on the substrate to directly form the plurality of coating layers.
In some preferred embodiments, the thin film evaporation method is implemented by using a thin film evaporation apparatus described below.
Referring to fig. 2 and fig. 3, an embodiment of the invention provides a thin film evaporation apparatus, including:
a
the
a
the
According to the film evaporation device, the target
In one embodiment, the
Preferably, the
The
In a preferred embodiment, the
Preferably, the substrate is a stainless steel substrate, and correspondingly, the
In another preferred embodiment, the substrate is sucked and fixed on the conveyor belt by a vacuum device, so that the substrate moves directionally along with the conveyor belt. The substrate may be a glass, quartz or polymer substrate.
Preferably, the length of each
Preferably, the distance between the substrate and the
Preferably, the
In a preferred embodiment, the
Target 302: cu(0.01~2.0)In(0~1.0)Ga(0~1.0)Se(0.01~3.0);
Target material 303: cu(0.01~2.0)In(0.01~1.5)Ga(0.01~1.0)Se(0.01~3.0)。
More preferably, the 3
target material 301: cu(0.01~0.5)In(0.01~0.5)Ga(0.5~1.0)Se(0.01~3.0);
Target 302: cu(1.0~2.0)In(0~0.5)Ga(0~0.5)Se(0.01~3.0);
Target material 303: cu(0.01~0.5)In(0.5~1.5)Ga(0.5~1.0)Se(0.01~3.0)。
Further preferably, the 3
target material 301: cu0.1In0.3Ga1.0Se0.5;
Target 302: cu2.0Se0.5;
Target material 303: cu0.1In0.5Ga1.0Se0.5。
In a preferred embodiment, the substrate to be evaporated sequentially passes through the 3
Referring to fig. 4, preferably, the
Preferably, the film evaporation device further includes a cooling device, the
Preferably, the film evaporation device further comprises a temperature adjusting device, preferably, the temperature adjusting device is arranged on one side of the
Optionally, since the Se element has high volatilization speed and is easy to be lost in the evaporation process, the thin film evaporation device also comprises a supply source of the Se element, so that the vapor pressure of Se vapor in the cavity is larger than 50kpa, and the Se element can be continuously and uniformly deposited on the substrate. Of course, the apparatus may be provided with a supply source of Cu, In, or Ga elements as appropriate.
Referring to fig. 5, in another embodiment, the
Preferably, the
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.