Method for manufacturing semiconductor device using plasma CVD process
11411120 · 2022-08-09
Assignee
Inventors
Cpc classification
H01L21/31
ELECTRICITY
H01L29/36
ELECTRICITY
H01L29/7869
ELECTRICITY
International classification
H01L29/66
ELECTRICITY
H01L29/786
ELECTRICITY
H01L29/36
ELECTRICITY
Abstract
A method for manufacturing a semiconductor device includes forming a semiconductor layer including an oxide semiconductor as a main component and forming an insulator layer on a surface of the semiconductor layer. The insulator layer includes silicon oside as a main component and has a hydrogen atom concentration that is less than or equal to 1×10.sup.21 atoms/cm.sup.3.
Claims
1. A method for manufacturing a semiconductor device, the method comprising: forming a semiconductor layer having a surface and including an oxide semiconductor as a main component; and forming an insulator layer on the surface of the semiconductor layer through a plasma CVD process using a source gas and an oxygen-containing gas, wherein: the insulator layer includes silicon oxide as a main component and has a hydrogen atom concentration that is less than or equal to 1×10.sup.21 atoms/cm.sup.3; the source gas contains silicon and an isocyanate group and does not contain hydrogen; and the forming of the insulator layer includes: setting a flow rate of the source gas to be greater than or equal to 0.005 sccm/cm.sup.2 and less than or equal to 0.1 sccm/cm.sup.2; generating a mixed gas by supplying the source gas and the oxygen-containing gas to a film formation space in which the insulator layer is formed; generating plasma from the mixed gas by supplying high frequency power to an electrode arranged in the film formation space, the high frequency power having a frequency of 13.56 MHz or 27.12 MHz at a level of greater than or equal to 0.07 W/cm.sup.2 and less than or equal to 1.5 W/cm.sup.2; and setting a ratio of the high frequency power supplied to the electrode to the flow rate of the source gas to be greater than or equal to 17 W/sccm and less than or equal to 72 W/sccm.
2. The method according to claim 1, wherein: the forming of the semiconductor layer includes forming at least one semiconductor layer including an oxide semiconductor as a main component, and the main component of the at least one semiconductor layer is any one of: an oxide semiconductor including indium (In) and oxygen (O); and an oxide semiconductor including zinc (Zn) and oxygen (O).
3. The method according to claim 1, wherein the forming of the semiconductor layer includes forming at least one semiconductor layer including an oxide semiconductor as a main component, and the main component of the at least one semiconductor layer is any one selected from a group consisting of InGaZnO, GaZnO, InZnO, InTiZnO, InAlZnO, ZnTiO, ZnO, ZnAlO, and ZnCuO.
4. The method according to claim 1, wherein the forming of the insulator layer includes using any one selected from a group consisting of Si(NCO).sub.4, Si(NCO).sub.3Cl, Si(NCO).sub.2Cl.sub.2, and Si(NCO)Cl.sub.3 as the source gas.
5. The method according to claim 1, wherein the forming of the insulator layer includes using any one selected from a group consisting of O.sub.2, O.sub.3, N.sub.2O, CO, and CO.sub.2 as the oxygen-containing gas.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF THE EMBODIMENTS
(13) Embodiments of a semiconductor device and a method for manufacturing a semiconductor device will now be described with reference to
(14) [Method for Manufacturing Semiconductor Device]
(15) A method for manufacturing a semiconductor device will now be described with reference to
(16) The method for manufacturing a semiconductor device includes forming a semiconductor layer and forming an insulator layer. The forming of a semiconductor layer includes forming a semiconductor layer having a surface and including an oxide semiconductor as a main component. The forming of an insulator layer includes forming an insulator layer on the surface of the semiconductor layer. The insulator layer includes silicon oxide (SiO.sub.2) as a main component and has a hydrogen atom concentration that is less than or equal to 1×10.sup.21 atoms/cm.sup.3.
(17) These processes form an insulator layer having a hydrogen atom concentration that is less than or equal to 1×10.sup.21 atoms/cm.sup.3. Thus, the characteristics of the semiconductor device are stabilized.
(18) The configuration of a sputtering apparatus, which is an example of an apparatus used to form a semiconductor layer, will now be described with reference to
(19) As shown in
(20) A cathode 13 is arranged in the vacuum chamber 11 at a position opposed to the support 12 to form a semiconductor layer. The cathode 13 includes a target 13a and a backing plate 31b. The main component of the target 13a is an oxide semiconductor. Preferably, the oxide semiconductor is any one selected from a group consisting of InGaZnO(IGZO), GaZnO, InZnO, InTiZnO, InAlZnO, ZnTiO, ZnO, ZnAlO, and ZnCuO. Ninety mass percent or more of the target 13a is the oxide semiconductor.
(21) The forming of a semiconductor layer may include forming a single semiconductor layer, the main component of which is any one selected from the group of oxide semiconductors described above or may include forming two or more semiconductor layers. More specifically, the forming of a semiconductor layer may include forming at least one semiconductor layer, the main component of which is an oxide semiconductor. In this case, each semiconductor layer includes any one selected from a group consisting of InGaZnO, GaZnO, InZnO, InTiZnO, InAlZnO, ZnTiO, ZnO, ZnAlO, and ZnCuO as a main component. More specifically, the main component of a semiconductor layer may be any one of an oxide semiconductor containing indium (In) and oxygen (O) and an oxide semiconductor containing zinc (Zn) and oxygen (O).
(22) The backing plate 31b is formed from a metal. The material forming the backing plate 31b is, for example, copper. The above-described target 13a is fixed to the backing plate 31b. The cathode 33 does not have to be entirely arranged in the vacuum chamber 11 as long as at least a sputtering surface of the target 13a is exposed in the vacuum chamber 11.
(23) The sputtering apparatus 10 includes a target power supply 14. The target power supply 14 is connected to the backing plate 31b. When the target power supply 14 applies voltage to the backing plate 31b, the voltage is applied to the target 13a through the backing plate 31b.
(24) The sputtering apparatus 10 further includes a gas discharge portion 15 and a sputtering gas supply portion 16. The gas discharge portion 15 depressurizes the film formation space, which is defined by the vacuum chamber 11, to a predetermined pressure. The gas discharge portion 15 includes, for example, a pump and a valve. The sputtering gas supply portion 16 supplies the vacuum chamber 11 with a sputtering gas used to generate plasma for sputtering the target 13a. The sputtering gas supply portion 16 is, for example, a mass flow controller that supplies the sputtering gas at a predetermined flow rate and is connected to a bomb located outside the sputtering apparatus 10. The sputtering gas supplied from the sputtering gas supply portion 16 may be, for example, a noble gas such as argon gas or may be an oxygen-containing gas such as oxygen gas.
(25) In the sputtering apparatus 10, when the film formation subject S is placed on the support 12, the gas discharge portion 15 depressurizes the film formation space to a predetermined pressure. After the sputtering gas supply portion 16 supplies the sputtering gas to the vacuum chamber 11, the target power supply 14 applies voltage to the target 13a through the backing plate 31b. Consequently, plasma is generated around the sputtering surface of the target 13a. Positive ions travel from the plasma toward the target 13a to sputter the sputtering surface of the target 13a. As a result, a semiconductor layer including an oxide semiconductor as a main component is formed on the film formation surface of the film formation subject S.
(26) As shown in rig. 2, a plasma CVD apparatus 20 includes a vacuum chamber 21 defining a film formation space in which an insulator layer is formed. A support 22 is arranged in the vacuum chamber 21 to support the film formation subject S or which a semiconductor layer 31 is formed. The support 22 is, for example, a stage that supports a laminated body of the semiconductor layer 31 and the film formation subject S.
(27) In the vacuum chamber 21, a dispersion portion 23 is arranged at a position opposed to the support 22. The dispersion portion 23 functions to disperse gas to form an insulator layer in the vacuum chamber 21. The dispersion portion 23 is, for example, a metal shower plate. The dispersion portion 23 is also an example of an electrode that is included in the plasma CVD apparatus 20.
(28) The plasma CVD apparatus 20 includes a gas discharge portion 24. The gas discharge portion 24 depressurizes the film formation space, which is defined by the vacuum chamber 21, to a predetermined pressure. In the same manner as the gas discharge portion 15 of the sputtering apparatus 10, the gas discharge portion 24 includes, for example, a pump and a valve.
(29) The plasma CVD apparatus 20 further includes a film formation gas supply unit 25, an oxygen-containing gas supply portion 26, a heater 27, and a high frequency power supply 28. The film formation gas supply unit 25 includes a constant temperature bath 25a, a reservoir 25b, and a film formation gas supply portion 25c. The constant temperature bath 25a defines an accommodation space accommodating the reservoir 25b and the film formation gas supply portion 25c and maintains the temperature of the accommodation space at a predetermined temperature. The reservoir 25b stores a film formation material M that is in a liquid state. The film formation material M is at vapor-liquid equilibrium in the reservoir 25b. The film formation gas supply portion 25c is a mass flow controller that is connected to the vacuum chamber 21 to supply the evaporated film formation material M to the vacuum chamber 21 at a predetermined flew rate. The film formation gas supply portion 25c supplies the gas of the film formation material M to the vacuum chamber 21 at a flow rate that is, for example, greater than or equal to 0.005 sccm/cm.sup.2 and less than or equal to 0.1 sccm/cm.sup.2.
(30) The film formation material M is, for example, tetraisocyanatesilane (Si(NCO).sub.4: TICS). The plasma CVD apparatus 20 forms an insulator layer through a plasma CVD process using tetraisocyanatesilane and oxygen. Tetraisocyanatesilane, which is the material of the insulator layer, does not contain hydrogen. This increases the reliability of the hydrogen atom concentration of the insulator layer being less than or equal to 1×10.sup.21 atoms/cm.sup.3.
(31) The film formation material M is not limited to Si(NCO).sub.4 and may be a material that contains silicon (Si) and an isocyanate group (NCO) and does not contain hydrogen. The film formation material M may be, for example, any one of Si(NCO).sub.3Cl, Si(NCO).sub.2Cl.sub.2, and Si(NCO)Cl.sub.3. In the plasma CVD apparatus 20, the source gas, which is obtained by evaporating the film formation material M, is supplied to the vacuum chamber 21. More specifically, in the forming of an insulator layer, any one selected from a group consisting of Si(NCO).sub.4, Si(NCO).sub.3Cl, Si(NCO).sub.2Cl.sub.2, and Si(NCO)Cl.sub.3 may be used as the source gas.
(32) The oxygen-containing gas supply portion 26 is connected to the vacuum chamber 21 via the heater 27. The oxygen-containing gas supply portion 26 is, for example, a mass flow controller that is connected to a bomb located outside the plasma CVD apparatus 20 to supply oxygen gas (O.sub.2) to the vacuum chamber 21 at a predetermined flow rate. The heater 27 heats the oxygen gas discharged from the oxygen-containing gas supply portion 26 to a predetermined temperature. The heater 27 heats the oxygen gas to a temperature that is, for example, higher than or equal to 50° C. and lower than or equal to 200° C.
(33) The oxygen-containing gas supply portion 26 may supply any one of O.sub.3, N.sub.2O, CO, and CO.sub.2 instead of O.sub.2 as the oxygen-containing gas. More specifically, the forming of an insulator layer may include using any one selected from a group consisting of O.sub.2, O.sub.3, N.sub.2O, CO, and CO.sub.2 as the oxygen-containing gas.
(34) The oxygen-containing gas supplied from the oxygen-containing gas supply portion 26 may be attenuated by an inert gas and supplied to the vacuum chamber 21. The inert gas may be, for example, N.sub.2/He, Ne, Ar, Kr, or Xe.
(35) When the high frequency power supply 28, which is connected to the dispersion portion 23, supplies power to the dispersion portion 23, a mixed gas of tetraisocyanatesilane gas and oxygen gas generates plasma around the dispersion portion 23 in the vacuum chamber 21. The high frequency power supply 28 supplies the dispersion portion 23 with high frequency power having a frequency of, for example, 13.56 MHz or 27.12 MHz at a level of greater than or equal to 0.07 W/cm.sup.2 and less than or equal to 1.5 W/cm.sup.7.
(36) It is preferred that when the insulator layer is formed, the ratio of power to the flow rate of the tetraisocyanatesilane gas be greater than or equal to 17 W/sccm. This increases the reliability of forming an insulator layer having a hydrogen atom concentration that is less than or equal to 1×10.sup.21 atoms/cm.sup.3.
(37) In the plasma CVD apparatus 20, when the film formation subject S on which the semiconductor layer 31 is formed is placed on the support 22, the gas discharge portion 24 depressurizes the vacuum chamber 21 to a predetermined pressure. After the film formation gas supply portion 25c supplies the tetraisocyanatesilane gas to the vacuum chamber 21 and the oxygen-containing gas supply portion 26 supplies oxygen gas to the vacuum chamber 21, the high frequency power supply 28 supplies power to the dispersion portion 23. As a result, plasma is generated around the dispersion portion 23 from the mixed gas described above. Active species in the plasma reach the semiconductor layer 31 to form an insulator layer including silicon oxide as the main component on the semiconductor layer 31.
(38) As described above. In an embodiment, the forming of an insulator layer may include generating a mixed gas by supplying tetraisocyanatesilane gas and oxygen gas to the film formation space, in which the insulator layer is formed, and generating plasma from the mixed gas by supplying power to the dispersion portion 23, which is an example of an electrode arranged in the film formation space. In such an embodiment, from the point in time when the plasma is generated, active species that are generated from tetraisocyanatesilane gas is oxidized by active species that are generated from the oxygen gas.
(39) [Thin-Film Transistor Structure]
(40) The structure of a semiconductor device will now be described with reference to
(41)
(42) The insulator layer 32 is arranged on the surface 313 of the semiconductor layer 31. The insulator layer 32 includes silicon oxide as a main component and has a hydrogen atom concentration that, is less than or equal to 1×10.sup.21 atoms/cm.sup.3. The insulator layer 32 covers the surface 31s of the semiconductor layer 31 and a portion of a gate insulator layer 35 that is not covered by the semiconductor layer 31.
(43) In the present embodiment, a single semiconductor layer is described as an example of the semiconductor layer 31. However, the semiconductor layer 31 may include at least one semiconductor layer. More specifically, the semiconductor layer 31 may include two or more semiconductor layers. It is preferred that the main component of each semiconductor layer be any one selected from a group consisting of InGaZnO, GaZnO, InZnO, InTiZnO, InAlZnO, ZnTiO, ZnO, ZnAlO, and ZnCuO.
(44) The thin-film transistor 30 includes the film formation subject S described above. The film formation subject S includes a substrate 33, a gate electrode 34, and the gate insulator layer 35. The gate electrode 34 is arranged on a portion of the surface of the substrate 33. The gate insulator layer 35 covers the entire gate electrode 34 and the surface of the substrate 33 that, is not covered by the gate electrode 34. The substrate 33 may be, for example, a resin substrate formed from various resins or a glass substrate. For example, molybdenum may be used as the material forming the gate electrode 34. The gate insulator layer 35 may be, for example, e silicon oxide layer or a laminated body of a silicon oxide layer and a silicon nitride layer.
(45) The semiconductor layer 31 is arranged on the surface of the gate insulator layer 35 so that the semiconductor layer 31 overlaps the gate electrode 34 in a direction in which the layers of the thin-film transistor 30 are stacked. The thin-film transistor 30 further includes a source electrode 36 and a drain electrode 37. The source electrode 36 and the drain electrode 37 are arranged next to each other with a predetermined gap between them in an arrangement direction (sideward direction in
(46) The thin-film transistor 30 further includes a protective film 38. The protective film 33 covers the source electrode 36, the drain electrode 37, and the insulator layer 32 that is exposed from both the source electrode 36 and the drain electrode 37. For example, silicon oxide may be used as the material forming the protective film 38.
Test Examples
(47) Test Examples will now be described with reference to
(48) [Laminated Body Structure]
(49) The structure of a test example of a laminated body 40 will now be described with reference to
(50) In the test example, the laminated body 40, which will be described below with reference to
(51) As shown in
(52) A first electrode layer 44A is arranged between the first part 43A and the second part 43B in the arrangement direction. The first electrode layer 44A covers a portion of the semiconductor layer 42, a portion of the first part 43A, and a portion of the second part 43B. A second electrode layer 44B is arranged between the first part 43A and the third part 43C in the arrangement direction. The second electrode layer 44B covers a portion of the semiconductor layer 42, a portion of the first part 43A, and a portion of the third part 43C.
(53) The main component of the semiconductor layer 42 is IGZO, and the main component of the insulator layer 43 is SiO.sub.2. The thickness of the semiconductor layer 42 is 50 nm. The thickness of the insulator layer 43 is 100 nm. The material forming the first electrode layer 44A and the second electrode layer 44B is Mo.
(54) To form the laminated body 40, a semiconductor layer is first formed on the surface of the glass substrate 41, and the semiconductor layer is etched via a mask to form the semiconductor layer 42. Then, a plasma CVD process is performed to form an insulator layer on the entire surface of the semiconductor layer 42 and a portion of the surface of the glass substrate 41 that is not covered by the semiconductor layer 42. The insulator layer is etched via a mask to form the insulator layer 43 that includes the first part 43A, the second part 43B, and the third part 43C. Subsequently, a metal layer is formed to cover the semiconductor layer 42 and the first part 43A, the second part 43B, and the third part 43C of the insulator layer 43. The metal layer is etched via a mask to form the first electrode layer 44A and the second electrode layer 44B.
(55) [Film Formation Condition]
(56) The semiconductor layer 42 and the insulator layer 43 of the laminated body 40 are formed under the following conditions.
(57) [Semiconductor Layer]
(58) TABLE-US-00001 Target InGaZnO Sputtering Gas Argon Gas/Oxygen Gas Sputtering Gas Flow Rate 80 sccm/6 sccm Pressure of Film Formation Space 0.3 Pa Power Applied to Target 240 W Area of Target 81 cm.sup.2 (diameter 4 inches)
(59) [Insulator Layer]
(60) TABLE-US-00002 Film Formation Gas Tetraisocyanatesilane (TICS) Film Formation Gas Flow Rate 55 sccm Oxygen Gas Flow Rate 2500 sccm Pressure of Film Formation Space 175 Pa High Frequency Power 400 W or higher and 4000 W or lower Area of Electrode 2700 cm.sup.2
(61) [Evaluation]
(62) [Concentration of Each Atom]
(63) When insulator layers were formed, the value of high frequency power was changed in a range from 400 W to 4000 W to obtain a number of laminated bodies that differ from each other in the value of high frequency power when the insulator layers are formed. The hydrogen atom concentration (atoms/cm.sup.3), the carbon atom concentration (atoms/cm.sup.3), and the oxygen atom concentration (atoms/cm.sup.3) were measured in the insulator layer of each laminated body. A secondary ion mass spectrometry (ADEPT1010, manufactured by ALVAC-PHI Inc.) was used to measure the concentration of each atom.
(64)
(65) As described above, the flow rate of the film formation gas is 55 scan. Thus, when high frequency power is 400 W, the ratio of the flow rate of the film formation gas to the high frequency power is 7 W/sccm. When high frequency power is 800 W, the ratio of the flow rate of the film formation gas to the high frequency power is 15 W/sccm. When high frequency power is 1000 W, the ratio of the flow rate of the film formation gas to the high frequency power is 18 W/sccm. When high frequency power is 1600 W, the ratio of the flow rate of the film formation gas to the high frequency power is 29 W/sccm. When high frequency power is 3000 W, the ratio of the flow rate of the film formation gas to the high frequency power is 55 W/sccm. When high frequency power is 4000 W, the ratio of the flow rate of the film formation gas to the high frequency power is 72 W/sccm. The measurement results of the hydrogen atom concentration verifies that when the ratio of the flow rate of the film formation gas to the high frequency power is greater than or equal to 17 W/sccm, the reliability of the hydrogen atom concentration of the insulator layer being less than or equal to 1×10.sup.21 atoms/cm.sup.3 increases.
(66) It is also verified that when tetraethoxysilane gas (TECS) is used as the film formation gas to form an insulator layer, the hydrogen atom concentration of the insulator layer is 4×10.sup.21 atoms/cm.sup.3, and that when silane gas (SiH.sub.4) is used as the film formation gas to form an insulator layer, the hydrogen gas concentration of the insulator layer 43 is 2×10.sup.21 atoms/cm.sup.3. The film formation conditions using each of TEOS gas and SiH.sub.4 gas were set as follows.
(67) [TEOS]
(68) TABLE-US-00003 Film Formation Gas Tetraethoxysilane (TEOS) Film Formation Gas Flow Rate 100 sccm Oxygen Gas Flow Rate 5000 sccm Pressure of Film Formation Space 175 Pa High Frequency Power 1600 W Area of Electrode 2700 cm.sup.2
(69) [SiH.sub.4]
(70) TABLE-US-00004 Film Formation Gas Silane (SiH.sub.4) Film Formation Gas Flow Rate 70 sccm N.sub.2O Gas Flow Rate 3500 sccm Pressure of Film Formation Space 200 Pa High Frequency Power 800 W Area of Electrode 2700 cm.sup.2
(71)
(72)
(73) [Refractive Index]
(74) The refractive index of the insulator layer of each laminated body was measured. A spectroscopic ellipsometer (M-2000V, manufactured by J. A. Woollam Co., Inc.) was used to measure the refractive index.
(75)
(76) [Film Stress]
(77) Film stress of the insulator layer of each laminated body was measured. A thin film stress measurement device (FLX-2000-A, manufactured by Toho Technology Inc.) was used to measure the film stress.
(78)
(79) [Carrier Concentration]
(80) The carrier concentration of the semiconductor layer of each laminated body was measured. A Hall effect measurement device (HL55001U, manufactured by Nanometrics Inc.) was used to measure the carrier concentration.
(81)
EXAMPLES
First Example
(82) A first example of a thin-film transistor was formed. The thin-film transistor has the structure that has been described with reference to
First Comparative Example
(83) A first comparative example of a thin-film transistor was formed using the same process as the first example except that the film formation condition of the insulator layer was the same as that of the test example using SiH.sub.4.
(84) [Evaluation]
(85) A semiconductor parameter analyzer (4155C, manufactured by Agilent Technologies) was used to measure transistor characteristics, that is, voltage (Vg)-current (Id) characteristics, of the thin-film transistor of the first example and the thin-film transistor of the first comparative example. The conditions for measuring the transistor characteristics were set as follows.
(86) TABLE-US-00005 Source Voltage 0 V Drain Voltage 5 V Gate Voltage from −15 V to 20 V Glass Substrate Temperature Room Temperature
(87) As shown in
(88) On the other hand, as shown in
(89) As described above, the embodiments of the semiconductor device and the method for manufacturing the semiconductor device have the advantages described below.
(90) (1) The insulator layer 32 having a hydrogen atoms concentration that is less than or equal to 1×10.sup.21 atoms/cm.sup.3 is formed. This stabilizes the characteristics of the thin-film transistor 30.
(91) (2) Tetraisocyanatesilane (TICS), which is the material of the insulator layer 32, does not include hydrogen. This increases the reliability of the hydrogen atom concentration of the insulator layer 32 being less than or equal to 1×10.sup.21 atoms/cm).
(92) (3) From the point in time when the plasma is generated, active species that are generated from tetraisocyanatesilane gas is oxidized by active species that are generated from oxygen gas.
(93) (4) When the ratio of power supplied to the dispersion portion 23 to the flow rate of tetraisocyanatesilane gas is greater than or equal to 17 W/sccm, the reliability of the hydrogen atom concentration of the insulator layer being less than or equal to atoms/cm.sup.3 increases.
(94) The embodiments may be modified as follows.
(95) The semiconductor device is not limited to the thin-film transistor 30 described above and may include a semiconductor element other than the thin-film transistor 30.