WO2010096172A1 - Procédé de traitement par plasma - Google Patents

Procédé de traitement par plasma Download PDF

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Publication number
WO2010096172A1
WO2010096172A1 PCT/US2010/000468 US2010000468W WO2010096172A1 WO 2010096172 A1 WO2010096172 A1 WO 2010096172A1 US 2010000468 W US2010000468 W US 2010000468W WO 2010096172 A1 WO2010096172 A1 WO 2010096172A1
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bias
fluorocarbon
recited
cfx
cfx4
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PCT/US2010/000468
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English (en)
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Hiroyuki Takaba
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Tokyo Electron Limited
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Priority to JP2011550137A priority Critical patent/JP2012518276A/ja
Priority to CN2010800082459A priority patent/CN102317752A/zh
Publication of WO2010096172A1 publication Critical patent/WO2010096172A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/517—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using a combination of discharges covered by two or more of groups C23C16/503 - C23C16/515
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32082—Radio frequency generated discharge
    • H01J37/32091—Radio frequency generated discharge the radio frequency energy being capacitively coupled to the plasma
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32192—Microwave generated discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32357—Generation remote from the workpiece, e.g. down-stream
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/3244—Gas supply means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/02312—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour
    • H01L21/02315—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma

Definitions

  • the present invention relates to semiconductor devices and their manufacturing methods. More specifically, it relates to a fluorocarbon (CFx) forming process for improving the adhesiveness of CFx layer with other metal or insulating layers while maintaining a low value of permittivity for the fluorocarbon (CFx) layer.
  • CFx fluorocarbon
  • low resistance wiring material e.g., copper (Cu)
  • Cu copper
  • low permittivity or lowk materials may be used to reduce the parasitic capacitance.
  • fluorine added carbon fluorocarbon: CFx
  • CFx fluorine added carbon
  • a conventional plasma reaction process is used for forming a fluorocarbon (CFx) layer with a low-permittivity.
  • the plasma reaction process is performed using a microwave plasma treatment device in which the plasma is generated by exciting a plasma gas, e.g., argon (Ar) or krypton (Kr), using a microwave from an external microwave source.
  • the deposition process is made using a plasma enhanced chemical vapor deposition (PE-CVD) method when a CF-series process gas such as, for example, CsFs or C ⁇ F ⁇ gas is introduced into a plasma region maintained under a pressure of at least about 50mTorr. This provides a higher film forming speed with regards to the etching speed for forming the fluorocarbon (CFx) layer.
  • PE-CVD plasma enhanced chemical vapor deposition
  • the fluorocarbon (CFx) formed under the above-mentioned forming condition using only one energy source, e.g., microwave plasma, as the plasma excitation source, may provide unfavorable results with regards to the insulating properties and the desorption gas characteristics of the CFx layer.
  • the adhesiveness of the CFx layer with the surface of other layers such as, for example, metals or insulating layers, may deteriorate at the time of deposition.
  • the present invention is proposed in view of the above aforementioned problems.
  • the present invention provides a process for forming a fluorocarbon (CFx) layer with superior insulating properties and desorption gas characteristics while maintaining a low value of permittivity.
  • a method for forming a fluorocarbon (CFx) insulating layer includes the step of applying a microwave power and an RF bias under a pressure of not less than 20mTorr and not more than 60mTorr.
  • a method for forming a fluorocarbon (CFx) insulating layer includes the step of applying a microwave power and an RF bias with a pressure under which the fluorocarbon layer does not deposit without applying the RF bias, wherein the pressure is not less than 20mTorr.
  • a method for manufacturing semiconductor devices having a fluorocarbon layer as an insulating layer includes the step of forming the fluorocarbon layer over a substrate using a plasma reaction process.
  • the forming step is performed when a microwave power and an RF bias are applied under a pressure ranging from 20mTorr to 60mTorr.
  • a method for forming a fluorocarbon layer using a plasma reaction process includes the steps of applying a microwave power and an RF bias,' and introducing oxygen (O) into a processing chamber in addition to a plasma excitation gas and a CF-series process gas.
  • Fig. 1 illustrates schematically an example of deposition rate as a function of pressure in a plasma reaction process.
  • Fig. 2 illustrates schematically dielectric constant curve of a fluorocarbon (CFx) layer as function of pressure.
  • Fig. 3 depicts a schematic diagram of an embodiment of an insulating layer forming device.
  • Fig. 4 illustrates target structure and a plan view of an experimental sample with its stress test results.
  • Fig. 5 illustrates contour maps used for measuring the thickness and refractive index of CFx4 samples.
  • Fig. 6 illustrates cross-sectional views of CFx experimental samples used for evaluating their surface morphology.
  • Fig. 7 illustrates leakage current as a function of applied field for various experimental samples.
  • Fig. 8 illustrates TDS intensity of various experimental samples.
  • Fig. 9 illustrates TDS intensity of various experimental samples.
  • Fig. 10 illustrates leakage current as function of RF bias for various experimental samples.
  • Fig. 11 illustrates leakage current as function of fluorocarbon layer thickness for various experimental samples.
  • Fig. 12 illustrates relative permittivity as function of pressure for various experimental samples.
  • Fig. 13 illustrates an average relative permittivity as function of pressure for various experimental samples.
  • Fig. 14 illustrates contour maps of an alternative embodiment.
  • Fig. 15 illustrates relative permittivity of various experimental samples as a function of refractive index.
  • This disclosure relates in general to semiconductor devices and their manufacturing process. More specifically, it relates to a new fluorocarbon (CFx) forming process for improving the adhesiveness of CFx layer with other metal or insulating layers while maintaining a low value of permittivity for the CFx layer.
  • CFx fluorocarbon
  • Embodiments of the present invention are directed to a process for forming a fluorocarbon (CFx) insulating layer with enhanced insulating properties and desorption gas characteristics to improve the adhesiveness of the CFx layer while maintaining a low value of permittivity (k: less than about 2.3).
  • CFx fluorocarbon
  • This is achieved by selecting a predetermined process condition where the fluorocarbon (CFx) layer may not be deposited without applying an RF bias with a microwave plasma power. In this way, the forming speed of the fluorocarbon deposition process is increased while the etching speed of the process is reduced.
  • the compositional ratio of a reactive byproduct, the conventional fluorocarbon (CFx) generated by the microwave plasma power may be minimized.
  • the predetermined process condition allows the majority of microwave plasma to excite the plasma gas, e.g., argon (Ar) gas, and also to maintain the plasma conditions.
  • the relative permittivity of the fluorocarbon (CFx) insulating layer is not adversely affected by the presence of the RF bias if the RF bias is applied within a few hundred watts.
  • a compositional ratio of carbon to fluorine (C/F) is about 0.9 to 1.0.
  • the fluorocarbon (CFx) layer is formed without applying the high-frequency RF bias, where the compositional ratio of carbon to fluorine (C/F) is about 1.1 to 1.2.
  • a barrier layer mainly composed of a metal element, such as, for example, titanium (Ti)
  • a plasma excitation source e.g., microwave power source
  • RF high-frequency
  • the fluorocarbon (CFx) layer formed under the above-mentioned condition does not show favorable results with regards to the insulating properties and the desorption gas characteristics of the CFx layer, despite its low permittivity (k ⁇ 2.3).
  • the deposition may occur when the pressure of the plasma gas is maintained at a pressure ranging from about 20mTorr to 60mTorr. As shown in Fig. 1, this pressure region is roughly divided into two sub-regions ⁇ l) the first sub-region with a pressure ranging from 20mTorr to 30mTorr and 2) the second sub-region with a pressure ranging from 30mTorr to 60mTorr.
  • the first sub-region also called “an etching plasma region" is a region where the deposition may not occur without applying the high-frequency (RF) power in combination with the microwave power source.
  • the second sub-region is a region where the deposition may occur without applying the high-frequency (RF) power, by applying the microwave power source as the only energy source.
  • RF high-frequency
  • CFx fluorocarbon
  • the fluorocarbon (CFx) etching speed may be reduced in addition to increase of the fluorocarbon forming speed. Since the forming speed and the etching speed in the plasma reaction process are directly related to the microwave power source, the microwave power source is set to generate a microwave power ranging from about IkW to 3.5kW at a frequency of 2.45 GHz.
  • the Fluorocarbon (CFx) layer formed in the above-mentioned pressure region provides favorable insulating properties and desorption gas characteristics.
  • the RF power source is applied at a frequency of about 400 kHz with an RF power ranging from about 2OW to 120W.
  • the relative permittivity of fluorocarbon (CFx) layer is not adversely affected by the presence of the RF bias source.
  • the fluorocarbon (CFx) layer with a relative permittivity of less than about 2.3 can be achieved when the pressure region is limited to a predetermined range.
  • a fluorocarbon (CFx) layer as function of pressure is schematically shown.
  • the fluorocarbon (CFx) insulating layer may be deposited by applying the RF power source in addition to the microwave power source, when the pressure of the plasma gas is maintained at or below 60mTorr.
  • the relative permittivity of the CFx layer tends to increase when the pressure becomes too low. This is mainly due to the fact that the amount of process gas, e.g., CF-series gas, that reacts with the generated plasma is relatively increased when the pressure of the plasma gas and the microwave power are low. As a result, the relative permittivity of the fluorocarbon (CFx) layer is increased when the pressure of the plasma gas becomes too low.
  • the predetermined range of the pressure is set to be within 20mTorr to 60mTorr, which is the same pressure range as the one used for obtaining fluorocarbon (CFx) layers with superior insulating properties and desorption gas characteristics.
  • the fluorocarbon (CFx) insulating layer is formed using an insulating layer forming device.
  • Fig. 3 illustrates a schematic diagram of an embodiment of an insulating layer forming device 30. As shown in this figure, the insulating layer forming device 30 includes a process vessel 50, a radial line slot antenna 62, and a mounting table 51.
  • An external microwave source 66 provides a microwave power of a predetermined frequency, e.g., 2.45 GHz, to the radial line slot antenna 62.
  • the microwave from the microwave source 66 causes excitation of a plasma gas, e.g., argon (Ar) gas, released into the plasma generation region Rl from gas supply ports 70.
  • the plasma gas is supplied from a plasma gas supply source 71 to the gas supply ports 70, via gas rings 72, which is then released into the plasma generation region Rl.
  • the insulating layer forming device 30 further includes a process gas supply structure 80, also called shower plate 80.
  • the plan view of the process gas supply structure 80 is also shown in Fig. 3.
  • the process gas supply structure 80 includes process gas supply pipes 81, disposed in between the plasma generation region Rl and the film forming region R2 as a grid facing the substrate W mounted on the mounting table 51.
  • the process gas supply pipes 81 may include an annular pipe 81a and a grid pipe 81b.
  • the annular pipe 81a is disposed annularly at an outer peripheral portion of the process gas supply structure 80.
  • the grid pipe 81b is disposed such that a plurality of matrix pipes is orthogonal with each other at an inner side of the annular pipe 81a.
  • a process gas supply source 84 is connected to the process gas supply pipes 81 through a gas pipe 85.
  • the process gas supply source 84 provides a mixture of argon (Ar) gas and a CF-series process gas, e.g., CsFs, as a diluted gas, to the process gas supply pipes 81 via the gas pipe 85.
  • the diluted gas is then discharged downwardly from the respective process gas supply ports 83 toward the film forming region R2.
  • the flow rate of a gas may be divided into two rates: 1) "sh-c” flow rate and 2) “sh-e” flow rate, depending on the location of process gas supply ports 83 on the shower plate 80.
  • the “sh-c” flow rate refers to the process gas supply ports 83 located at the center of the shower plate 80.
  • the “sh-e” flow rate refers to the process gas supply ports 83 located at the edge portion of the shower plate 80.
  • fluorocarbon (CFx) insulating layer In order to evaluate insulating properties, the adhesion, and also the reliable operation of fluorocarbon (CFx) insulating layer, several experimental samples are manufactured according to the process described in the present disclosure. The experimental samples are then subjected to different tests for evaluating the above-mentioned properties. In each of the experimental samples a fluorocarbon (CFx4) insulating layer is formed by applying the high-frequency RF power source and the microwave plasma source.
  • the following setting conditions are used to form the following fluorocarbon layers ⁇ 1) CFx4 layers; a microwave power of about IkW to 3.5kW at a frequency of 2.45 GHz, a high-frequency RF power of about 2OW to 120W at a frequency of 400kHz,, 2) CFx2 layers; a microwave power of about 1.5kW at a frequency of 2.45 GHz, without applying any high -frequency RF bias and formed under a low pressure, less than 30mTorr and 3) CFx layers; a microwave power of about 3kW at a frequency of 2.45 GHz, without applying any high-frequency RF bias and formed under a pressure of about 50mTorr.
  • the structure used for these evaluations includes a first amorphous carbon layer, a fluorocarbon (CFx4) layer, a second amorphous carbon layer, and a hermetic cap layer.
  • the first amorphous carbon layer is formed on a bulk silicon (Si) substrate while the second amorphous carbon layer is formed over the fluorocarbon (CFx4) layer.
  • Both amorphous carbon layers have a thickness of about 10 nm and are formed in the etching plasma region where a high-frequency (RF) bias, from an external RF power source 53 (please refer to Fig.
  • RF high-frequency
  • the RF bias has a frequency of 400 kHz with an RF power of about 120W.
  • the fluorocarbon (CFx4) layer is also formed under the same forming condition in the etching plasma region. Therefore, the same RF bias source, as the one used for forming the amorphous carbon layers, is applied to the substrate W.
  • the hermetic cap layer is formed to react with desorption gas generated from the CFx4 layer.
  • a pre -evaluation annealing is then performed at a temperature of about 350 0 C for a period of 24 hours.
  • the experimental sample is subjected respectively to the stress test, the blister test, and the tape test.
  • the stress test is conducted at a temperature of about 400 °C for a period of 2 hours.
  • This experimental sample passed the stress test at all deposition layers, amorphous carbon layers and the CFx4 layer.
  • a plan view of the experimental sample after adhering scotch tape to its surface is also shown in Fig. 4. Similar to the stress test, all the layers formed in the etching plasma region with applied RF bias passed the blister test and the tape test. This means that no blisters and peeling-off of the layers were observed for this sample.
  • CFx4 fluorocarbon
  • Table I summarizes the average value, the minimum value, the maximum value, and the non-uniformity value obtained from the contour maps with regards to the thickness and the refractive index of the experimental samples.
  • FIG. 6 cross-sectional views of two experimental samples, taken from different points compared to the center of their respective wafers, are shown.
  • the cross-sectional views of both experimental samples are shown in the upper and lower side of Fig. 6.
  • the cross-sectional views are taken at two points with following coordinates ⁇ i) A(O, 0) and 2) B(-135, 0).
  • the cross sectional-views of the CFx4 experimental sample are taken at three points where the first two points have the same coordinates as the one used for the CFx sample (A(O, 0), B(-135, O)), while the third point has the following coordinates C(-150, 0).
  • Fig. 6 cross-sectional views of two experimental samples, taken from different points compared to the center of their respective wafers.
  • the cross-sectional views of both experimental samples are shown in the upper and lower side of Fig. 6.
  • the cross-sectional views are taken at two points with following coordinates ⁇ i) A(O, 0) and
  • the experimental sample with the CFx4 insulating layer has less dents and raises compared to the experimental sample with CFx insulating layer. Therefore, the surface morphology of CFx4 insulating layer is improved compared to the case of CFx layer. As a result, a smoother surface for the CFx4 insulating layer is obtained.
  • the leakage current as a function of applied field is shown for various experimental samples.
  • the leakage current is measured at a point of thermal stress where a heat treatment is conducted at a temperature of about 400 "C for a period of 2 hours.
  • Three experimental samples! CFx, CFx2, and CFx4, are formed for this evaluation.
  • both CFx and CFx2 insulating layers are formed without applying any high-frequency RF bias.
  • the CFx insulating layer is formed under a pressure of about 50mTorr while the CFx2 insulating layer is formed under a low pressure (less than 30mTorr).
  • the high-frequency RF bias is applied for forming the experimental sample with CFx4 insulating layer under the same condition as those described in paragraph [0027]. [0036]
  • the experimental sample with the CFx4 insulating layer has a lower leakage current when the applied voltage is within a range of about -2MV/cm to -0.5MV/cm.
  • Table II summarizes the value of leakage current (Jg@1.5MV/cm) for each experimental sample when the applied electric field is about 1.5MV/cm. As shown in Table II, the CFx4 insulating layer has a lower leakage Current value at l. ⁇ MV/cm.
  • CFx, CFx2, and CFx4 Three experimental samples (CFx, CFx2, and CFx4) are formed according to the fluorocarbon forming process of the present invention and then subjected to the thermal desorption spectroscopy (TDS) measurement.
  • TDS thermal desorption spectroscopy
  • This experiment is performed to detect the molecular weight or atomic weight of fluorine (F) in each experimental sample.
  • a thermal desorption spectroscopy of each sample is measured and the results are shown in Fig. 8.
  • fluorine (F) gas with the mass of 19 is detected.
  • Table V summarizes the setting conditions for forming our best current CFx4 samples.
  • the leakage current as a function of RF bias is shown for four experimental samples. All the experimental samples were manufactured using the film forming process of the present invention with the setting conditions as described in paragraph [0027]. Three experimental samples with the CFx4 insulating layers were formed where the RF bias was respectively set at the following powers: OW, 6OW, and 120W. The fourth experimental sample includes a CFx layer as the insulating layer and the RF power was set to OW for this sample. As shown in Fig. 10, the leakage current tends to decrease when the RF bias power increases. It should be noted that the leakage current values are measured when the applied voltage is set to lMV/cm (Jg@lMV/cm). [0042]
  • Fig. 11 illustrates the leakage current as a function of fluorocarbon (CFx4) layer thickness.
  • CFx4 fluorocarbon
  • three set of experimental samples were manufactured. In each set, five experimental samples with approximately the same fluorocarbon (CFx4) thickness layer were formed.
  • the average thickness of fluorocarbon (CFx4) insulating layer for the first, second, and third set of experimental samples are respectively 85.49nm, 137.11nm, and 190.26nm.
  • the leakage current values are measured when the applied voltage is set to lMV/cm (Jg@lMV/cm).
  • CFx4 layer as a function of pressure is shown for various experimental samples.
  • two set of experimental samples were formed using the insulating layer forming device 30. In each set, three experimental samples are formed under the following pressures : 25mTorr, 30mTorr, and 35mTorr.
  • the RF bias in the first and second set is respectively set to 9OW and 120W.
  • the measurement results of relative permittivity are shown in Fig. 12. As shown in this figure, the higher the setting condition for pressure, the higher is the value of relative permittivity.
  • the average relative permittivity as a function of pressure is shown in Fig. 13 for various experimental samples. As shown in this figure, the minimum average value of 2.38 is obtained at a pressure of 22mTorr, while the maximum average value of 2.62 is obtained at a pressure of 28mTorr. According to this result, the pressure value of 22mTorr provides the lowest value of relative permittivity. This means that the best value of pressure used for forming fluorocarbon (CFx4) insulating layers is about 22mTorr. [0045]
  • an alternative embodiment is evaluated to improve even further the properties of the fluorocarbon (CFx4) insulating layer.
  • oxygen (O) is introduced through the gas ring 72 into the process vessel 50 of the insulating layer forming device 30.
  • two experimental samples (#1 and #2) with exactly the same setting conditions, except for the oxygen (O) gas, are manufactured.
  • Table VII summarizes the setting conditions for both experimental samples. As discussed previously, "sh-c”, “sh-e”, represent respectively the flow rate of a gas at the center and edge of the shower plate 80, while “gr” represent the flow rate of the gas at the gas rings 72.
  • contour maps of both experimental samples used for measuring the refractive index are shown. As shown in this figure, the maximum, minimum, and average values of refractive index are lower for the experimental sample #2 where the oxygen (O) gas is added into the atmosphere on the process vessel 50. This results in a lower permittivity (lowk) for the second experimental sample.
  • Table VIII summarizes the thickness, the refractive index, and the relative permittivity (k) of both experimental samples. As shown in this Table, the thickness value and the relative permittivity (k) are also lower when the oxygen is added into the atmosphere. This evaluation confirms that a lower value of permittivity may be obtained using oxygen (O).
  • the experimental samples of each set are subjected to an accelerated test, also called "Mist bath", for evaluation. Therefore, after forming the fluorocarbon (CFx, CFx2, or CFx4) insulating layers of each set, the experimental samples of each set are put into a constant temperature, e.g., 80 °C, at a high humidity bath, e.g., 85% (H2O). To conduct our experiment, the first sample of each set is not subjected to the accelerated test. Then, the second sample of each set is subjected to the accelerated test by putting the experimental sample into the Mist bath for a period of 1 to 10 minutes. The last experimental sample in each set is also subjected to the accelerated test for a period of 100 minutes. [0049]
  • Fig. 15 illustrates relative permittivity (k-value) as a function of refractive index for each set of experimental sample. It is known that the smaller is the change in refractive index of an insulating layer, kept at a constant temperature in a high humidity environment, the better is their insulating properties and therefore their overall reliabilities. [0050]
  • the fluorocarbon (CFx4) insulating layers of the third set of experimental sample are formed by applying an RF bias and also by adding nitrogen (N2) gas into the atmosphere. By adding nitrogen (N2) into the atmosphere, the nitrogen (N2) atoms get excited, thereby emitting light toward the surface of the CFx4 insulating layer. This results in a curing or modifying effect on the fluorocarbon (CFx) insulating layer, which leads in turn to a smaller variation in refractive index and consequently in relative permittivity.

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  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Drying Of Semiconductors (AREA)
  • Formation Of Insulating Films (AREA)
  • Chemical Vapour Deposition (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

L'invention concerne un procédé de formation d'une couche de fluorocarbone au moyen d'un processus de réaction par plasma comprenant une étape consistant à appliquer une énergie à micro-ondes et une polarisation RF. L'énergie à micro-ondes et la polarisation RF sont appliquées à une pression comprise entre 20 mTorr et 60 mTorr.
PCT/US2010/000468 2009-02-17 2010-02-17 Procédé de traitement par plasma WO2010096172A1 (fr)

Priority Applications (2)

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JP2011550137A JP2012518276A (ja) 2009-02-17 2010-02-17 プラズマ処理方法
CN2010800082459A CN102317752A (zh) 2009-02-17 2010-02-17 等离子体处理方法

Applications Claiming Priority (2)

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US20797309P 2009-02-17 2009-02-17
US61/207,973 2009-02-17

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WO2010096172A1 true WO2010096172A1 (fr) 2010-08-26

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KR (1) KR20110129401A (fr)
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CN105793023A (zh) * 2013-12-06 2016-07-20 米其林企业总公司 制造用于硫化轮胎的模具的模制元件的方法
US11904352B2 (en) 2019-05-17 2024-02-20 Jiangsu Favored Nanotechnology Co., Ltd. Low dielectric constant film and preparation method thereof

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* Cited by examiner, † Cited by third party
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CN110129769B (zh) * 2019-05-17 2021-05-14 江苏菲沃泰纳米科技股份有限公司 疏水性的低介电常数膜及其制备方法
KR20240037610A (ko) * 2022-09-15 2024-03-22 충남대학교산학협력단 고유전 비정질 불소화 탄소 박막 게이트 유전층을 갖는 반도체 소자 및 그 제조방법

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US6492068B1 (en) * 1999-01-12 2002-12-10 Kawasaki Steel Corporation Etching method for production of semiconductor devices

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JP2751851B2 (ja) * 1995-02-09 1998-05-18 日本電気株式会社 フッ素化非晶質炭素膜の製造方法
JP4054123B2 (ja) * 1997-11-20 2008-02-27 東京エレクトロン株式会社 プラズマ成膜方法
JP4355039B2 (ja) * 1998-05-07 2009-10-28 東京エレクトロン株式会社 半導体装置及び半導体装置の製造方法
US6746970B2 (en) * 2002-06-24 2004-06-08 Macronix International Co., Ltd. Method of forming a fluorocarbon polymer film on a substrate using a passivation layer
JP2006135303A (ja) * 2004-10-05 2006-05-25 Tokyo Electron Ltd プラズマ成膜方法及びプラズマ成膜装置、並びにプラズマ成膜装置に用いられる記憶媒体
JP5082411B2 (ja) * 2006-12-01 2012-11-28 東京エレクトロン株式会社 成膜方法

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US6136722A (en) * 1997-10-15 2000-10-24 Nec Corporation Plasma etching method for forming hole in masked silicon dioxide
US6492068B1 (en) * 1999-01-12 2002-12-10 Kawasaki Steel Corporation Etching method for production of semiconductor devices

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105793023A (zh) * 2013-12-06 2016-07-20 米其林企业总公司 制造用于硫化轮胎的模具的模制元件的方法
US11904352B2 (en) 2019-05-17 2024-02-20 Jiangsu Favored Nanotechnology Co., Ltd. Low dielectric constant film and preparation method thereof

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JP2012518276A (ja) 2012-08-09
KR20110129401A (ko) 2011-12-01
CN102317752A (zh) 2012-01-11
TWI510665B (zh) 2015-12-01
TW201100580A (en) 2011-01-01

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