CN112349738A - Semiconductor device, forming method thereof and image sensor - Google Patents
Semiconductor device, forming method thereof and image sensor Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/1462—Coatings
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/14632—Wafer-level processed structures
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14643—Photodiode arrays; MOS imagers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
- H01L27/14685—Process for coatings or optical elements
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
- H01L27/14687—Wafer level processing
Abstract
The invention provides a semiconductor device, a forming method thereof and an image sensor. The forming method of the semiconductor device comprises the following steps: providing a substrate, and forming densely distributed inverted triangular grooves on one side surface of the substrate; carrying out maskless etching and/or maskless ion implantation pretreatment on the substrate to roughen the surface of the inverted triangular groove; and etching the roughened surface of the inverted triangular groove by an acid method to form a textured structure on the roughened surface of the inverted triangular groove. The densely distributed inverted triangular grooves form a large-suede structure on the surface of the substrate, the optical path length in the image sensor silicon wafer is expanded, the effective optical path length is prolonged along with the extension in the silicon wafer, and the light absorption efficiency is improved. The surface of the inverted triangular groove forms a suede structure which is a small suede structure, so that the reflection times of light in the substrate are further increased, and the quantum efficiency of the device is greatly improved.
Description
Technical Field
The invention belongs to the technical field of integrated circuit manufacturing, and particularly relates to a semiconductor device, a forming method of the semiconductor device and an image sensor.
Background
For silicon-based semiconductor devices (e.g., optoelectronic devices), the surface reflectivity of silicon is high, and if the silicon surface is not treated, the reflectivity of the silicon can reach over 40% for visible light and over 60% for near-infrared light. The crystalline silicon has such a high reflectivity to light that the quantum efficiency of a related photoelectric device prepared by the crystalline silicon is not ideal, and the application field and the use performance of the photoelectric product are finally severely restricted.
The principle of the application of optoelectronic chips is the absorption of light by the material. However, the absorption of light by the material is conditional. Only if the light wave has energy greater than the forbidden band width will the material absorb light. The absorption efficiency of crystalline silicon to photons is gradually reduced from visible light to near infrared light, and even though crystalline silicon has good absorption efficiency to the visible light range of a traditional CMOS Image Sensor (CIS), the problem of photon absorption by silicon becomes more and more prominent as light waves are from visible light to near infrared light, and attention of engineering technicians are paid to the crystalline silicon. The absorption efficiency of the material for photons can be improved by increasing the thickness of silicon, but the increase of the thickness of silicon brings huge challenges to the semiconductor process, and the silicon is not cost-effective. Therefore, it is required to further improve the absorption of light by the semiconductor device.
Disclosure of Invention
The invention aims to provide a semiconductor device, a forming method thereof and an image sensor, which can improve the light absorption efficiency of the semiconductor device and the quantum efficiency of the device.
The invention provides a method for forming a semiconductor device, which comprises the following steps:
providing a substrate, and forming densely distributed inverted triangular grooves on one side surface of the substrate; on a cross section vertical to the substrate, the cross section of the inverted triangular groove is in an inverted triangle shape;
carrying out maskless etching and/or maskless ion implantation pretreatment on the substrate to roughen the surface of the inverted triangular groove;
and etching the roughened surface of the inverted triangular groove by an acid method to form a textured structure on the roughened surface of the inverted triangular groove.
Further, the acid etching is performed by using a mixed solution of hydrofluoric acid and nitric acid.
Further, the maskless etching adopts plasma etching, and etching gas includes: SF6、C4F8And Ar, and said SF6The gas flow is 70 sccm-140 sccm, C4F8The gas flow is 75sccm to 100sccm, and the Ar gas flow is 15sccm to 45 sccm.
Furthermore, in the maskless ion implantation, the implantation energy range of the ions is 5 keV-45 keV, and the implantation dosage range of the ions is 5 multiplied by 1014ions/cm2～1×1016ions/cm2。
Further, after the surface of the roughened inverted triangular groove forms a textured structure, the method further comprises the following steps: and forming a filling layer for filling the inverted triangular groove.
Further, after the surface of the roughened inverted triangular groove forms a textured structure, the method further comprises the following steps:
forming a first anti-reflection film layer, a second anti-reflection film layer and a third anti-reflection film layer which sequentially cover the surfaces of the inverted triangular grooves;
wherein the refractive index of the third antireflection film layer, the refractive index of the second antireflection film layer, and the refractive index of the first antireflection film layer are increased in this order.
Furthermore, the densely distributed inverted triangular grooves are distributed in an inverted rectangular pyramid array.
Further, the method for forming the inverted triangular groove comprises the following steps:
forming a patterned photoresist on the surface of the substrate;
etching the substrate by a dry method by taking the patterned photoresist as a mask to form an inverted trapezoidal groove;
and further etching the substrate by adopting wet etching to form the inverted triangular groove.
Furthermore, in the dry etching process, etching is performedThe etching gas comprises polymer gas C4F8The polymer gas C4F8The etching gas accounts for 15-30% of the total etching gas, and the ratio of the source power to the bias power ranges from 4:1 to 6: 1; in the wet etching process, TMAH solution is used for etching, the mass concentration of the TMAH solution is 20-25%, and the wet etching time is 1-12 min.
Further, an HK dielectric layer and a first insulating layer are sequentially formed on one side surface of the substrate.
Further, the method for forming the inverted triangular groove comprises the following steps:
forming a patterned photoresist on the surface of the first insulating layer;
etching the first insulating layer, the HK dielectric layer and the substrate with partial thickness by taking the patterned photoresist as a mask to form an inverted trapezoidal groove;
etching the inverted trapezoidal groove by a wet method, wherein the HK dielectric layer is not easy to etch, and an initial inverted triangular groove with a top opening shrinking inwards and a brim is formed;
forming a filler in the initial inverted triangular trench;
and removing the cap peak by dry etching to form the inverted triangular groove.
Further, the method for forming the inverted triangular groove comprises the following steps:
forming a first patterned photoresist on the surface of the first insulating layer; the patterned first photoresist is provided with a first window;
dry etching the first insulating layer and the HK dielectric layer to expose the substrate by taking the patterned first photoresist as a mask;
forming a patterned second photoresist on the substrate and the first insulating layer, the patterned second photoresist having a second window; the second window is smaller than the first window;
the patterned second photoresistors positioned at two sides of the second window at least cover part of the exposed substrate with the width of the part;
etching the substrate by a dry method by taking the patterned second photoresist as a mask to form an inverted trapezoidal groove;
removing the patterned second photoresist;
and further etching the substrate by adopting wet etching to form the inverted triangular groove.
Further, a second insulating layer is formed on one side surface of the substrate, and the method for forming the inverted triangular trench includes:
forming a patterned photoresist on the surface of the second insulating layer;
taking the patterned photoresist as a mask, and etching the second insulating layer by a dry method to expose the substrate;
dry etching the substrate with partial thickness to form an opening;
and performing wet etching on the opening to form the inverted triangular groove.
The present invention also provides a semiconductor device comprising:
the device comprises a substrate, wherein inverted triangular grooves which are densely distributed are formed in the surface of one side of the substrate; on a cross section vertical to the substrate, the cross section of the inverted triangular groove is in an inverted triangle shape; the surface of the inverted triangular groove is of a suede structure.
Further, the semiconductor device further comprises a filling layer filling the inverted triangular groove.
Further, the semiconductor device further includes:
a first anti-reflection film layer, a second anti-reflection film layer and a third anti-reflection film layer which sequentially cover the surfaces of the inverted triangular grooves;
wherein the refractive index of the third antireflection film layer, the refractive index of the second antireflection film layer, and the refractive index of the first antireflection film layer are increased in this order.
The present invention also provides an image sensor comprising:
the photoelectric device comprises a substrate, a photoelectric diode and a plurality of inverted triangular grooves, wherein the substrate is provided with a substrate front surface and a substrate back surface which are opposite, the photoelectric diode is formed on one side close to the substrate front surface, and the inverted triangular grooves which are densely distributed are formed on the substrate back surface; on a cross section vertical to the substrate, the cross section of the inverted triangular groove is in an inverted triangle shape; the surface of the inverted triangular groove is of a suede structure.
Further, the image sensor further includes:
a first anti-reflection film layer, a second anti-reflection film layer and a third anti-reflection film layer which sequentially cover the surfaces of the inverted triangular grooves;
wherein the refractive index of the third antireflection film layer, the refractive index of the second antireflection film layer and the refractive index of the first antireflection film layer are increased in sequence;
furthermore, densely distributed pixel unit areas are formed on the substrate, deep groove isolation is distributed between adjacent pixel unit areas, a plurality of inverted triangular grooves are formed in each pixel unit area, the third antireflection film layer also covers the back surface of the substrate, and a color filter layer and a lens layer are sequentially distributed above each pixel unit area.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a semiconductor device, a forming method thereof and an image sensor; the forming method of the semiconductor device comprises the following steps: providing a substrate, and forming densely distributed inverted triangular grooves on one side surface of the substrate; on a cross section vertical to the substrate, the cross section of the inverted triangular groove is in an inverted triangle shape; carrying out maskless etching and/or maskless ion implantation pretreatment on the substrate to roughen the surface of the inverted triangular groove; and etching the roughened surface of the inverted triangular groove by an acid method to form a textured structure on the roughened surface of the inverted triangular groove. The densely distributed inverted triangular grooves form a large-suede structure on the surface of the substrate, the optical path length in the image sensor silicon wafer is expanded, the effective optical path length is prolonged along with the extension in the silicon wafer, and the light absorption efficiency is improved. The surface of the inverted triangular groove forms a suede structure which is a small suede structure, so that the reflection times of light in the substrate are further increased, and the quantum efficiency of the device is greatly improved.
Drawings
Fig. 1 is a flow chart of a method for forming a semiconductor device according to an embodiment of the invention.
FIG. 2 is a schematic diagram of forming densely-distributed inverted triangular trenches according to an embodiment of the present invention;
FIG. 3 is a schematic view of a textured structure formed on the surface of the inverted triangular groove according to the embodiment of the present invention;
FIG. 4 is a schematic diagram of a filling layer formed in an inverted triangular trench according to an embodiment of the present invention;
FIG. 5 is a schematic view of a textured structure formed on the surface of an inverted triangular trench in a substrate according to an embodiment of the present invention;
fig. 6a to 6c illustrate a first method for forming an inverted triangular trench according to an embodiment of the present invention.
Fig. 7a to 7e illustrate a second method for forming an inverted triangular trench according to an embodiment of the present invention.
Fig. 8a to 8e illustrate a third method for forming an inverted triangular trench according to an embodiment of the present invention.
Fig. 9a to 9d illustrate a fourth method for forming an inverted triangular trench according to an embodiment of the present invention.
Fig. 10 is a schematic structural diagram of the image sensor provided in this embodiment.
Detailed Description
Based on the above research, embodiments of the present invention provide a semiconductor device, a method of forming the same, and an image sensor. The invention is described in further detail below with reference to the figures and specific examples. The advantages and features of the present invention will become more apparent from the following description. It is to be noted, however, that the drawings are designed in a simplified form and are not to scale, but rather are to be construed in an illustrative and descriptive sense only and not for purposes of limitation.
An embodiment of the present invention provides a method for forming a semiconductor device, as shown in fig. 1, including:
s1, providing a substrate, and forming densely distributed inverted triangular grooves on one side surface of the substrate; on a cross section vertical to the substrate, the cross section of the inverted triangular groove is in an inverted triangle shape;
s2, performing pretreatment of maskless etching and/or maskless ion implantation on the substrate to roughen the surface of the inverted triangular groove;
s3, performing acid etching on the roughened surface of the inverted triangular groove to form a textured structure on the roughened surface of the inverted triangular groove.
As shown in fig. 2, a substrate 10 is provided, the substrate 10 being, for example, a silicon substrate. A HK (high dielectric constant) dielectric layer 21 and a first insulating layer 22 are sequentially formed on one side surface of the substrate 10, the HK dielectric layer 21 being, for example, at least one of aluminum oxide, hafnium oxide, zirconium oxide, or other HK (high dielectric constant) thin films; the HK dielectric layer 21 can increase the light transmittance of the substrate surface and also reduce the parasitic capacitance. The first insulating layer 22 is, for example, a silicon oxide layer or a silicon nitride layer. Forming densely distributed inverted triangular grooves Va on one side surface of the substrate 10; the cross-sectional shape of the inverted triangular trench Va is inverted triangular in a cross section perpendicular to the substrate 10. Illustratively, the densely distributed inverted triangular grooves are distributed in an inverted rectangular pyramid (inverted pyramid) array. The densely distributed inverted triangular grooves form a large-suede structure on the surface of the substrate, so that incident light perpendicular to the substrate irradiates the side faces of the inverted triangular grooves according to Snell's law, enters the substrate through refraction, and then is totally reflected inside the substrate, and the structure greatly reduces the condition that the incident light irradiates the surface of the inverted substrate and is reflected outside the substrate. The optical path length in the silicon chip is expanded, and the effective optical path length is prolonged along with the extension in the substrate, so that the light absorption efficiency is increased. The number of reflection times of light in the substrate is increased, so that the capture capacity of the substrate surface to incident light energy is enhanced, namely, the reflection loss of the light energy is reduced, and the absorption and conversion efficiency of the device to the light is improved.
As shown in fig. 2 and 3, the substrate 10 is subjected to a pretreatment of maskless etching and/or maskless ion implantation to roughen the surface of the inverted triangular trench Va. In the process of roughening the surface of the inverted triangular groove Va by the pretreatment, the maskless etching is plasma etching or non-plasma etching. If adoptedThe plasma etching increases the surface roughness of the silicon wafer, and the gas adopted by the plasma etching comprises: SF6、C4F8And Ar, and said SF6The gas flow is 70 sccm-140 sccm, C4F8The gas flow is 75sccm to 100sccm, and the Ar gas flow is 15sccm to 45 sccm. The pretreatment increases the roughness of the surface of the silicon wafer, and is beneficial to the subsequent etching texturing process by an acid method so as to form more textured structures on the roughened surfaces of the inverted triangular grooves Va. If non-plasma etching is adopted to increase the roughness of the surface of the silicon wafer, the non-plasma etching comprises wet etching, dry etching and etching of physical, chemical and electrochemical methods capable of generating a micro concave-convex structure on the surface of the silicon. In the maskless ion implantation, the substrate 10 is N-type and the ions are phosphorus ions, or the substrate 10 is P-type and the ions are boron ions. The implantation energy of the ions is 5 keV-45 keV, and the implantation dosage of the ions is 5 x 1014ions/cm2～1×1016ions/cm2。
And performing acid etching (acid texturing) on the roughened surface of the inverted triangular groove Va to form a textured structure A, specifically a small textured structure, on the roughened surface of the inverted triangular groove. And etching by adopting an acid mixed solution of hydrofluoric acid and nitric acid by adopting an acid method, and forming irregular depressions which are densely distributed along the direction vertical to the substrate on the surface of the inverted triangular groove by utilizing isotropic etching to form a small densely distributed suede structure. Illustratively, the acid mixed solution includes hydrofluoric acid, nitric acid, and deionized water. The mass content of hydrofluoric acid and nitric acid in the acid mixed solution is 10-45% and 15-55%. The substrate 10 is put into the acid mixed solution for texturing, the texturing temperature is, for example, 5 ℃ to 20 ℃, and the texturing time is 80s to 180 s. The method relieves the etching pressure of dry etching, the prepared inverted triangular suede structure greatly increases the photoelectric conversion efficiency of silicon, and no metal pollution is introduced, so that the method is suitable for being applied to semiconductor devices.
Densely distributed inverted triangular trenches are formed on one side surface of the substrate, and the structure is also called as Cell Deep Trench Isolation (CDTI). The surface of the inverted triangular groove forms a suede structure, so that the reflection times of light in the substrate are further increased, and the quantum efficiency of the device is greatly improved. The surface of the substrate (such as a silicon substrate) prepared by the method is generally black, and is generally called as black silicon.
As shown in fig. 4, after the textured structure a is formed on the roughened surface of the inverted triangular groove, the method further includes: a filling layer 30 filling the inverted triangular trench is formed. The filling layer 30 is, for example, a silicon oxide layer 30, and the filling layer 30 may also cover the surface of the first insulating layer 22. Specifically, the filling layer 30 may be formed by a chemical vapor deposition process, and then the filling layer 30 is chemically and mechanically polished, so that the filling layer 30 may be maintained to a certain thickness as required.
In other embodiments, after forming the textured structure on the roughened surface of the inverted triangular groove, the method may further include: forming a first antireflection film layer, a second antireflection film layer and a third antireflection film layer which sequentially cover the surfaces of the inverted triangular grooves; the refractive index of the third antireflection film layer, the refractive index of the second antireflection film layer and the refractive index of the first antireflection film layer are sequentially increased to ensure that light is transmitted from the light-thinning medium to the light-dense medium, so that the incident light reflectivity is reduced to the minimum, and the absorption and conversion efficiency of the semiconductor device to light is improved. The film layers covering the grooves can be four or more, the refractive index of the film layers covering the inverted triangular grooves is sequentially reduced from the position close to the side walls of the inverted triangular grooves outwards, so that light can enter the optically denser medium from the optically thinner medium, the light refraction is increased, the light reflection is reduced, the number of the specific film layers is not limited, and the film layers are configured according to actual needs. In the film layers covering the inverted triangular groove, the outermost film layer may further fill the inverted triangular groove, for example, when the film layers covering the inverted triangular groove are three layers, the third antireflection film layer may further fill the inverted triangular groove in addition to the second antireflection film layer.
Fig. 5 shows another embodiment, in which no HK (high dielectric constant) dielectric layer and no first insulating layer are disposed on the substrate, densely-distributed inverted triangular trenches are formed on the substrate 10, textured structures are formed on the surfaces of the inverted triangular trenches, and the filling layer 30 is formed in the inverted triangular trenches.
The steps of the method for forming the inverted triangular trench of the semiconductor device of the present embodiment will be described below with reference to fig. 6a to 9 d.
Referring to fig. 6a to 6c, a first method of forming an inverted triangular trench according to the present embodiment will be described.
As shown in fig. 6a, providing a substrate 10, wherein the substrate 10 is, for example, a silicon substrate, and a patterned photoresist 51 is formed on a surface of the substrate 10; as shown in fig. 6B, the substrate 10 is dry-etched by using the patterned photoresist 51 as a mask to form an inverted trapezoidal trench 41a, the bottom angle a of the inverted trapezoidal trench 41a at the bottom of the trench is in the range of 110 to 120 °, and the side surface inclination angle B of the inverted trapezoidal trench 41a is in the range of 60 to 70 °. The power, pressure, gas and time during the dry etching process are controlled to form the inverted trapezoid trench 41 a. Specifically, the polymer gas C is controlled4F8And the ratio of the source power to the bias power, polymer gas C4F8Accounts for 15-30% of the total etching gas, and the ratio of the source power to the bias power ranges from 4:1 to 6: 1. As shown in fig. 6c, the inverted triangular trench 41b is formed by wet etching, for example, the inverted triangular trench 41b is formed by wet etching using a tetramethylammonium hydroxide (TMAH) solution, the mass concentration of the TMAH solution is 20% to 25%, the wet etching time is 1min to 12min, and the wet etching is performed. The first method for forming the inverted trapezoidal trench is to form the inverted triangular trench 41b with good absorption of incident light by combining dry etching with wet etching, the densely distributed inverted triangular trenches 41b are densely distributed on the surface of the substrate 10, and the CDTI has good shape uniformity and process controllability.
A second method of forming the inverted triangular trench is described below with reference to fig. 7a to 7 e.
As shown in fig. 7a to 7b, providing a substrate 10, wherein the substrate 10 is, for example, a silicon substrate, and an HK (high dielectric constant) dielectric layer 21 and a first insulating layer 22 are sequentially formed on one side surface of the substrate 10, and the HK dielectric layer 21 is, for example, at least one of aluminum oxide, hafnium oxide, zirconium oxide, or other HK (high dielectric constant) thin films; the first insulating layer 22 is, for example, a silicon oxide layer or a silicon nitride layer. Semiconductor devices are used as photoelectric materials, and HK dielectric layers are often used, and can increase the light transmittance of the surface of a substrate and reduce parasitic capacitance. A patterned photoresist 52a is formed on the surface of the first insulating layer 22. And etching the first insulating layer 22, the HK dielectric layer 21 and the substrate 10 with partial thickness by using the patterned photoresist 52a as a mask to form an inverted trapezoidal groove 42a, wherein the side surface inclination angle E of the inverted trapezoidal groove 42a is in the range of 50-70 degrees.
As shown in fig. 7c and 7d, the inverted trapezoidal trench 42a is etched by using a wet TMAH solution to form an initial inverted triangular trench 42a ', because the HK dielectric layer 21 is dense and the HK dielectric layer 21 is not easily etched during the wet etching process, the HK dielectric layer 21 and the first insulating layer 22 on both sides of the top of the initial inverted triangular trench 42 a' form a cap peak P, and the cap peak P affects the optical path to be removed. Forming a filler in the initial inverted triangular trench 42 a'; specifically, a BARC (Bottom Anti-Reflective Coating) is deposited in the initial inverted triangular trench 42 a' using Chemical Vapor Deposition (CVD). The BARC has good flow and can fill the original inverted triangular trench 42 a' well. A patterned photoresist 52b is formed over the first insulating layer 22, and the patterned photoresist 52b has an opening cross-sectional width equal to or greater than the maximum cross-sectional width of the original inverted triangular trench 42 a' in a cross-section perpendicular to the substrate 10. As shown in fig. 7d and 7e, the patterned photoresist 52b is used as a mask to remove the protruding cap peak P by dry etching, so as to form the inverted triangular trench 42 b.
The second method for forming the inverted triangular groove introduces that the HK dielectric layer 21 and the first insulating layer 22 are formed on the substrate, the HK dielectric layer 21 is not easy to etch in the wet etching process, after the cap peak P is formed, the cap peak P is removed through dry etching, the inverted triangular groove 42b with good incident light absorption is finally formed, the densely distributed inverted triangular grooves 42b are densely distributed on the surface of the substrate 10, and the CDTI shape uniformity and the process controllability are good.
A third method for forming the inverted triangular trench is described below with reference to fig. 8a to 8 e.
As shown in fig. 8a and 8b, a substrate 10 is provided, and an HK dielectric layer 21 and a first insulating layer 22 are sequentially formed on one side surface of the substrate 10. Forming a patterned first photoresist 53a on the surface of the first insulating layer 22, wherein the patterned first photoresist 53a has a first window; and dry etching the first insulating layer 22 and the HK dielectric layer 21 by using the patterned first photoresist 53a as a mask to expose the substrate 10. As shown in fig. 8c and 8d, a patterned second photoresist 53b is formed on the substrate 10 and the first insulating layer 22, the patterned second photoresist 53b having a second window; the second window is smaller than the first window. The patterned second photoresist 53b on both sides of the second window at least covers a part of the width of the exposed substrate 10. And dry etching the substrate 10 by using the patterned second photoresist 53b as a mask to form an inverted trapezoidal groove 43a, wherein the side-face inclination angle C of the inverted trapezoidal groove 43a ranges from 50 degrees to 75 degrees, removing the patterned second photoresist 53b, and exposing the top D of the substrate 10 at two sides of the inverted trapezoidal groove 43 a.
As shown in fig. 8e, the inverted triangular trench 43b is formed by wet etching, for example, the inverted triangular trench 42b is formed by wet etching using a tetramethylammonium hydroxide (TMAH) solution, the mass concentration of the TMAH solution is 20% to 25%, the wet etching time is 1min to 12 min.
In the third method for forming the inverted triangular trench, the top D of the substrate 10 at the two sides of the inverted trapezoidal trench 43a is exposed by patterning the photoresist twice, i.e., the top D of the substrate 10 at the partial width is not covered by the HK dielectric layer 21, so that the problem of the cap peak P occurring when the HK dielectric layer 21 is not etched in the process of forming the inverted triangular trench by wet etching is avoided in fig. 7 c. The densely distributed inverted triangular trenches 43b are densely distributed on the substrate 10, and the formed CDTI has good shape uniformity and process controllability.
A fourth method for forming the inverted triangular trench is described below with reference to fig. 9a to 9 d.
As shown in fig. 9a and 9b, a substrate 10 is provided, the substrate 10 is, for example, a silicon substrate, a second insulating layer 23 is formed on one side surface of the substrate 10, and the second insulating layer 23 is, for example, a silicon oxide layer or a silicon nitride layer. A patterned photoresist 54 is formed on the surface of the second insulating layer 23. And dry etching the second insulating layer 23 to expose the substrate 10 by using the patterned photoresist 54 as a mask. As shown in fig. 9c, the substrate 10 is dry etched by a part of the thickness to form an opening K, and the cross section of the opening is rectangular in shape in the cross section perpendicular to the substrate. As shown in fig. 9d, wet etching is performed on the opening K, specifically, a TMAH solution is used to wet etch the substrate, so as to form an inverted triangular trench 44b, and the side surface inclination angle F of the inverted triangular trench 44b is 54.7 °.
The fourth method for forming the inverted triangular groove introduces that the inverted triangular groove is formed by adopting a dry method and a wet method under the condition that no HK dielectric layer exists on the substrate.
The present embodiment also provides a semiconductor device including:
the device comprises a substrate, wherein inverted triangular grooves which are densely distributed are formed in the surface of one side of the substrate; on a cross section vertical to the substrate, the cross section of the inverted triangular groove is in an inverted triangle shape; the surface of the inverted triangular groove is of a suede structure.
Specifically, the semiconductor device further includes: a first antireflection film layer, a second antireflection film layer and a third antireflection film layer, wherein the first antireflection film layer and the second antireflection film layer sequentially cover the surface of the inverted triangular groove, and the third antireflection film layer covers the second antireflection film layer and fills the inverted triangular groove;
wherein the refractive index of the third antireflection film layer, the refractive index of the second antireflection film layer, and the refractive index of the first antireflection film layer are increased in this order.
Fig. 10 is a schematic structural diagram of the image sensor provided in this embodiment. As shown in fig. 10, the present embodiment also provides an image sensor including:
a substrate 60, said substrate 60 having an opposite substrate front side f1And a substrate back surface f2Near the front side f of the substrate1A side shapeForming a photodiode, and forming densely distributed inverted triangular grooves V on the back surface of the substrate; on a cross section perpendicular to the substrate 60, the cross-sectional shape of the inverted triangular groove V is an inverted triangle; the surface of the inverted triangular groove V is of a suede structure.
The image sensor further includes: a first antireflection film layer (not shown), a second antireflection film layer (not shown), and a third antireflection film layer 63 which cover the surfaces of the inverted triangular grooves in this order; wherein the refractive index of the third antireflection film layer, the refractive index of the second antireflection film layer, and the refractive index of the first antireflection film layer are increased in this order.
Specifically, the third antireflection film layer 63 may fill the inverted triangular groove, and the third antireflection film layer 63 further covers the back surface f of the substrate2(ii) a Densely distributed pixel unit areas A are formed on the substrate 60, deep trench isolation 66 is distributed between adjacent pixel unit areas A, and low-refractive-index deep trench isolation 66 is used between pixels to inhibit transverse crosstalk. A plurality of inverted triangular grooves V are formed in each pixel unit area A, and a color filter layer 64 and a lens layer 65 are sequentially distributed above the third antireflection film layer 63 in each pixel unit area; the color filter layer 64 is positioned above the third antireflection film layer 63, and the color filter layer includes color filter units densely distributed; the lens layer 65 is positioned above the color filter layer 64, and the lens layer 65 includes densely distributed microlenses; wherein the color filter units, the microlenses and the pixel unit regions correspond one-to-one in a direction perpendicular to the substrate. Front side f of the substrate1 A dielectric layer 67 is formed on one side, and a metal layer 68 is distributed in the dielectric layer 67.
The image sensor provided by the embodiment has very low reflectivity and high absorption efficiency. The densely distributed inverted triangular grooves V form a large-suede structure on the surface of the substrate, the optical path length in the image sensor silicon wafer is expanded, the effective optical path length is prolonged along with the extension in the silicon wafer, and the light absorption efficiency is improved. The surface of the inverted triangular groove V is of a small suede structure, so that the reflection times of light in the substrate are further increased, and the quantum efficiency of the device is greatly improved.
In summary, the present invention provides a semiconductor device, a method of forming the same, and an image sensor; the forming method of the semiconductor device comprises the following steps: providing a substrate, and forming densely distributed inverted triangular grooves on one side surface of the substrate; on a cross section vertical to the substrate, the cross section of the inverted triangular groove is in an inverted triangle shape; carrying out maskless etching and/or maskless ion implantation pretreatment on the substrate to roughen the surface of the inverted triangular groove; and etching the roughened surface of the inverted triangular groove by an acid method to form a textured structure on the roughened surface of the inverted triangular groove. The densely distributed inverted triangular grooves form a large-suede structure on the surface of the substrate, the optical path length in the image sensor silicon wafer is expanded, the effective optical path length is prolonged along with the extension in the silicon wafer, and the light absorption efficiency is improved. The surface of the inverted triangular groove forms a suede structure which is a small suede structure, so that the reflection times of light in the substrate are further increased, and the quantum efficiency of the device is greatly improved.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the method disclosed by the embodiment, the description is relatively simple because the method corresponds to the device disclosed by the embodiment, and the relevant points can be referred to the description of the method part.
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.
Claims (19)
1. A method of forming a semiconductor device, comprising:
providing a substrate, and forming densely distributed inverted triangular grooves on one side surface of the substrate; on a cross section vertical to the substrate, the cross section of the inverted triangular groove is in an inverted triangle shape;
carrying out maskless etching and/or maskless ion implantation pretreatment on the substrate to roughen the surface of the inverted triangular groove;
and etching the roughened surface of the inverted triangular groove by an acid method to form a textured structure on the roughened surface of the inverted triangular groove.
2. The method for forming a semiconductor device according to claim 1, wherein the acid etching is etching using a mixed solution of hydrofluoric acid and nitric acid.
3. The method of forming a semiconductor device according to claim 1, wherein the maskless etching employs plasma etching, and etching gas includes: SF6、C4F8And Ar, and said SF6The gas flow is 70 sccm-140 sccm, C4F8The gas flow is 75sccm to 100sccm, and the Ar gas flow is 15sccm to 45 sccm.
4. The method of claim 1, wherein the maskless ion implantation has an implantation energy of 5keV to 45keV and an implantation dose of 5 x 1014ions/cm2～1×1016ions/cm2。
5. The method of forming a semiconductor device according to claim 1, further comprising, after forming a textured structure on the roughened surface of the inverted triangular trench:
and forming a filling layer for filling the inverted triangular groove.
6. The method of forming a semiconductor device according to claim 1, further comprising, after forming a textured structure on the roughened surface of the inverted triangular trench:
forming a first anti-reflection film layer, a second anti-reflection film layer and a third anti-reflection film layer which sequentially cover the surfaces of the inverted triangular grooves;
wherein the refractive index of the third antireflection film layer, the refractive index of the second antireflection film layer, and the refractive index of the first antireflection film layer are increased in this order.
7. The method of forming a semiconductor device according to claim 1, wherein the densely distributed inverted triangular trenches are distributed in an inverted rectangular pyramid array.
8. The method for forming a semiconductor device according to any one of claims 1 to 7, wherein the method for forming the inverted triangular trench comprises:
forming a patterned photoresist on the surface of the substrate;
etching the substrate by a dry method by taking the patterned photoresist as a mask to form an inverted trapezoidal groove;
and further etching the substrate by adopting wet etching to form the inverted triangular groove.
9. The method for forming a semiconductor device according to claim 8, wherein in the dry etching process, the etching gas includes a polymer gas C4F8The polymer gas C4F8The etching gas accounts for 15-30% of the total etching gas, and the ratio of the source power to the bias power ranges from 4:1 to 6: 1; in the wet etching process, TMAH solution is used for etching, the mass concentration of the TMAH solution is 20-25%, and the wet etching time is 1-12 min.
10. The method for forming a semiconductor device according to any one of claims 1 to 7, wherein an HK dielectric layer and a first insulating layer are formed on one side surface of the substrate in this order.
11. The method for forming a semiconductor device according to claim 10, wherein the method for forming the inverted triangular trench comprises:
forming a patterned photoresist on the surface of the first insulating layer;
etching the first insulating layer, the HK dielectric layer and the substrate with partial thickness by taking the patterned photoresist as a mask to form an inverted trapezoidal groove;
etching the inverted trapezoidal groove by a wet method, wherein the HK dielectric layer is not easy to etch, and an initial inverted triangular groove with a top opening shrinking inwards and a brim is formed;
forming a filler in the initial inverted triangular trench;
and removing the cap peak by dry etching to form the inverted triangular groove.
12. The method for forming a semiconductor device according to claim 10, wherein the method for forming the inverted triangular trench comprises:
forming a first patterned photoresist on the surface of the first insulating layer; the patterned first photoresist is provided with a first window;
dry etching the first insulating layer and the HK dielectric layer to expose the substrate by taking the patterned first photoresist as a mask;
forming a patterned second photoresist on the substrate and the first insulating layer, the patterned second photoresist having a second window; the second window is smaller than the first window;
the patterned second photoresistors positioned at two sides of the second window at least cover part of the exposed substrate with the width of the part;
etching the substrate by a dry method by taking the patterned second photoresist as a mask to form an inverted trapezoidal groove;
removing the patterned second photoresist;
and further etching the substrate by adopting wet etching to form the inverted triangular groove.
13. The method for forming a semiconductor device according to any one of claims 1 to 7, wherein a second insulating layer is formed on one side surface of the substrate, and the method for forming the inverted triangular trench includes:
forming a patterned photoresist on the surface of the second insulating layer;
taking the patterned photoresist as a mask, and etching the second insulating layer by a dry method to expose the substrate;
dry etching the substrate with partial thickness to form an opening;
and performing wet etching on the opening to form the inverted triangular groove.
14. A semiconductor device, comprising:
the device comprises a substrate, wherein inverted triangular grooves which are densely distributed are formed in the surface of one side of the substrate; on a cross section vertical to the substrate, the cross section of the inverted triangular groove is in an inverted triangle shape; the surface of the inverted triangular groove is of a suede structure.
15. The semiconductor device of claim 14, further comprising a fill layer filling the inverted triangular trench.
16. The semiconductor device according to claim 14, further comprising:
a first anti-reflection film layer, a second anti-reflection film layer and a third anti-reflection film layer which sequentially cover the surfaces of the inverted triangular grooves;
wherein the refractive index of the third antireflection film layer, the refractive index of the second antireflection film layer, and the refractive index of the first antireflection film layer are increased in this order.
17. An image sensor, comprising:
the photoelectric device comprises a substrate, a photoelectric diode and a plurality of inverted triangular grooves, wherein the substrate is provided with a substrate front surface and a substrate back surface which are opposite, the photoelectric diode is formed on one side close to the substrate front surface, and the inverted triangular grooves which are densely distributed are formed on the substrate back surface; on a cross section vertical to the substrate, the cross section of the inverted triangular groove is in an inverted triangle shape; the surface of the inverted triangular groove is of a suede structure.
18. The image sensor of claim 17, further comprising:
a first anti-reflection film layer, a second anti-reflection film layer and a third anti-reflection film layer which sequentially cover the surfaces of the inverted triangular grooves;
wherein the refractive index of the third antireflection film layer, the refractive index of the second antireflection film layer, and the refractive index of the first antireflection film layer are increased in this order.
19. The image sensor of claim 18,
the substrate is provided with densely distributed pixel unit areas, deep groove isolation is distributed between adjacent pixel unit areas, a plurality of inverted triangular grooves are formed in each pixel unit area, the third antireflection film layer further covers the back face of the substrate, and a color filter layer and a lens layer are sequentially distributed above each pixel unit area.
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| CN116435325A (en) * | 2023-06-13 | 2023-07-14 | 合肥晶合集成电路股份有限公司 | Backside illuminated image sensor and method of forming the same |
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