JP4216003B2 - Method for manufacturing semiconductor device - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a semiconductor film having an amorphous structure by a plasma CVD method, a semiconductor device having a circuit including a thin film transistor (hereinafter referred to as TFT) using the semiconductor film, and a method for manufacturing the semiconductor device. For example, the present invention relates to an electro-optical device typified by a liquid crystal display panel and an electronic apparatus in which such an electro-optical device is mounted as a component.
[0002]
Note that in this specification, a semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and an electro-optical device, a semiconductor circuit, and an electronic device are all semiconductor devices.
[0003]
[Prior art]
A thin film transistor (hereinafter referred to as TFT) is known as a typical semiconductor element using a semiconductor film having a crystal structure. TFT is attracting attention as a technique for forming an integrated circuit on an insulating substrate such as glass, and a drive circuit integrated liquid crystal display device or the like is being put into practical use. In a conventional technique, a semiconductor film having a crystal structure is obtained by heating an amorphous semiconductor film deposited by a plasma CVD method or a low pressure CVD method, or a laser annealing method (a technique for crystallizing a semiconductor film by laser light irradiation). It is produced by.
[0004]
The semiconductor film having a crystal structure manufactured in this way is an aggregate of a large number of crystal grains, and the crystal orientation is oriented in an arbitrary direction and cannot be controlled, which is a factor that limits the characteristics of the TFT. In order to solve such problems, the technique disclosed in Japanese Patent Laid-Open No. 7-183540 is to add a metal element that promotes crystallization of a semiconductor film such as nickel to produce a semiconductor film having a crystal structure. In addition to the effect of lowering the heating temperature required for crystallization, it is possible to increase the orientation of crystal orientation in a single direction. When a TFT is formed using a semiconductor film having such a crystal structure, not only the field-effect mobility is improved, but also the subthreshold coefficient (S value) is reduced, and the electrical characteristics can be dramatically improved. ing.
[0005]
By using a metal element that promotes crystallization, nucleation in crystallization can be controlled, so the film quality obtained is uniform compared to other crystallization methods in which nucleation is random, ideally. It is desirable to completely remove metal elements or reduce them to an acceptable range. However, since a metal element that promotes crystallization is added, the metal element remains in the film of the semiconductor film having a crystal structure or on the film surface, and there is a problem in that the characteristics of the obtained element are varied. . As an example, there is a problem that an off current increases in a TFT and varies between individual elements. That is, the metal element that promotes crystallization becomes unnecessary once a semiconductor film having a crystal structure is formed.
[0006]
Gettering using phosphorus is effectively used as a technique for removing a metal element that promotes crystallization from a specific region in a semiconductor film having a crystal structure. For example, the metal element can be easily removed from the channel formation region by adding phosphorus to the source / drain region of the TFT and performing heat treatment at 450 to 700 ° C.
[0007]
[Problems to be solved by the invention]
Phosphorus is an ion doping method (PH_ThreeEtc. is dissociated with plasma, and ions are accelerated by an electric field and injected into a semiconductor, and basically refers to a method in which ion mass separation is not performed). The phosphorus concentration required for gettering is 1 × 10²⁰/cm^ThreeThat's it. Addition of phosphorus by the ion doping method causes the semiconductor film having a crystal structure to become amorphous. However, an increase in the phosphorus concentration hinders recrystallization by subsequent annealing, which is a problem. Further, the addition of high-concentration phosphorus is problematic because it increases the processing time required for doping and decreases the throughput in the doping process.
[0008]
Furthermore, the concentration of boron necessary to invert the conductivity type of phosphorus added to the source / drain regions of the p-channel TFT must be 1.5 to 3 times, which makes recrystallization difficult. As a result, the resistance of the source / drain regions is increased, which is a problem.
[0009]
Further, if the gettering is not sufficient in the substrate and the gettering varies, there is a slight difference, that is, a variation in each TFT characteristic. In the case of a transmissive liquid crystal display device, if the TFTs arranged in the pixel portion have variations in electrical characteristics, there will be variations in the voltage applied to each pixel electrode, resulting in variations in the amount of transmitted light, resulting in display unevenness. It will be reflected in the eyes of the observer.
[0010]
In addition, for a light emitting device using an OLED, a TFT is an essential element for realizing an active matrix driving method. Therefore, in a light emitting device using an OLED, at least a TFT that functions as a switching element and a TFT that supplies current to the OLED are provided in each pixel. An on-current (I) of a TFT that is electrically connected to the OLED and supplies current to the OLED regardless of the circuit configuration of the pixel and the driving method._on), The luminance of the pixel is determined. For example, in the case of white display on the entire surface, there is a problem in that the luminance varies if the on-current is not constant.
[0011]
The present invention is a means for solving such a problem, and after obtaining a semiconductor film having a crystal structure using a metal element that promotes crystallization of a semiconductor film, the metal element remaining in the film is removed. It aims at providing the technique which removes effectively.
[0012]
[Means for Solving the Problems]
The gettering technique is positioned as a main technique in the manufacturing technique of an integrated circuit using a single crystal silicon wafer. Gettering is known as a technique for reducing the impurity concentration of an active region of an element by segregating metal impurities taken into a semiconductor to gettering sites with some energy. It is roughly divided into extrinsic gettering and intrinsic gettering. The extrinsic gettering provides a gettering effect by applying a strain field and chemical action from the outside. In this case, gettering in which a high concentration of phosphorus is diffused from the back surface of the single crystal silicon wafer corresponds to this, and gettering using the above-described phosphorus can be regarded as a kind of extrinsic gettering.
[0013]
On the other hand, intrinsic gettering is known as utilizing a strain field of lattice defects involving oxygen generated inside a single crystal silicon wafer. The present invention pays attention to intrinsic gettering using such lattice defects or lattice distortions, and adopts the following means to apply to a semiconductor film having a crystal structure of about 10 to 100 nm in thickness. To do.
[0014]
The present invention includes a step of forming a first semiconductor film having a crystal structure on an insulating surface using a metal element that promotes crystallization of a semiconductor, and a film serving as an etching stopper (barrier) on the first semiconductor film. A layer), a step of forming a second semiconductor film containing a noble gas source (gettering site) on the barrier layer, a step of gettering a metal element at the gettering site, And a step of removing the semiconductor film.
[0015]
The present invention uses the plasma CVD method as a step of forming the gettering site, forms a film using monosilane, a rare gas element, and hydrogen as a source gas, and has an amorphous structure containing a rare gas element at a high concentration. The semiconductor film is typically an amorphous silicon film. Further, disilane or trisilane may be used instead of monosilane. Note that the plasma CVD method can clean a film formation chamber (also referred to as a chamber) with a gas, and therefore requires less maintenance than the sputtering method, and is a film formation method suitable for mass production.
[0016]
In addition, since hydrogen is used as one of the source gases as compared with a case where hydrogen is not used as one of the source gases, the concentration of hydrogen contained in the film is reduced. Further, as compared with a case where hydrogen is not used as one of the source gases, the concentration of fluorine contained in the film is reduced by forming a film using hydrogen as one of the source gases.
[0017]
The structure of the invention relating to the method for manufacturing a semiconductor film disclosed in this specification is as follows.
Monosilane, a rare gas, and hydrogen are introduced as source gases into the film formation chamber, and plasma is generated, so that the rare gas element is 1 × 10 6.¹⁸/ Cm^Three~ 1x10^{twenty two}/ Cm^ThreeAnd a semiconductor film having an amorphous structure is formed over the surface of the semiconductor film.
[0018]
In the above structure, when the plasma is generated, the pressure in the deposition chamber is preferably 2.666 Pa to 133.3 Pa, and preferably less than 53.32 Pa (0.4 Torr).
[0019]
In the above structure, the flow rate ratio of hydrogen to rare gas (H₂/ Noble gas) is controlled to 0.2-5.
[0020]
In the above configuration, the RF power density for generating the plasma is 0.0017 W / cm.²~ 1W / cm²It is characterized by being. 1W / cm²If the RF power is higher than that, a film formation failure such that the film does not become a film but becomes a powder or a hemispherical float occurs in the film is likely to occur.
[0021]
In the above structure, monosilane, a rare gas element, and hydrogen are used as a raw material gas, and the ratio (monosilane: rare gas) is set to 0.1: 99.9 to 1: 9, preferably 1:99 to 5:95. It is characterized by being controlled to form a semiconductor film containing a rare gas element at a high concentration and having an amorphous structure, typically an amorphous silicon film. Further, disilane or trisilane may be used instead of monosilane. The film forming temperature is preferably 300 ° C to 500 ° C.
[0022]
Monosilane (flow rate 2 sccm), argon (flow rate 198 sccm) and hydrogen (10 sccm) are used as source gases, the ratio (monosilane: rare gas) is controlled to 1:99, the film formation temperature is 350 ° C., and the film formation pressure is 6. FIG. 17 shows the experimental results obtained by measuring the argon / silicon intensity ratio near the surface of the amorphous silicon film formed under the film forming conditions of 665 Pa (0.05 Torr) and RF power of 50 W by TXRF to obtain the argon concentration.
[0023]
In the above structure, the fluorine concentration in the semiconductor film is 2 × 10¹⁶/ Cm^Three~ 8x10¹⁶/ Cm^Three, Preferably 1 × 10¹⁵/ Cm^Three~ 1x10¹⁷/ Cm^ThreeIt is characterized by being.
[0024]
Further, the structure of the invention related to the method for manufacturing a semiconductor device disclosed in this specification is as follows.
A first step of forming a first semiconductor film having an amorphous structure on an insulating surface;
A second step of adding a metal element to the first semiconductor film having the amorphous structure;
A third step of crystallizing the first semiconductor film to form a first semiconductor film having a crystal structure;
A fourth step of forming a barrier layer on the surface of the first semiconductor film having the crystal structure;
A fifth step of forming a second semiconductor film containing a rare gas element on the barrier layer by a plasma CVD method;
A sixth step of removing or reducing the metal element in the first semiconductor film having a crystal structure by gettering the metal element to the second semiconductor film;
And a seventh step of removing the second semiconductor film.
[0025]
In the above structure, the second semiconductor film is formed by a plasma CVD method in which monosilane, a rare gas, and hydrogen are introduced as source gases into a deposition chamber to generate plasma.
[0026]
In the above structure, the metal element is a metal element that promotes crystallization of silicon, and is a kind selected from Fe, Ni, Co, Ru, Rh, Pd, Os, Ir, Pt, Cu, Au, or There are multiple species.
[0027]
In each of the above structures, the rare gas element is one or more selected from He, Ne, Ar, Kr, and Xe.
[0028]
(Experiment 1)
Here, the plasma CVD method was used, and the RF power density dependence of the argon concentration in the amorphous silicon film formed on the semiconductor substrate using monosilane, argon element, and hydrogen as source gases was examined.
[0029]
First, the semiconductor substrate is transferred into the chamber, heated and maintained at 300 ° C., and the pressure in the chamber is adjusted by an exhaust system so as to be 66.65 Pa (0.5 Torr). Next, SiH is introduced into the chamber from the gas introduction system._FourThe gas was introduced at a flow rate of 100 sccm and the discharge frequency was 27.12 MHz from the high-frequency power source, the input RF power was 20 W (RF power density 0.033 W / cm²(Electrode area 600cm²The first amorphous silicon film was formed by the plasma CVD method while performing the discharge of)). The first amorphous silicon film is a reference.
[0030]
  Next, a second amorphous silicon film having a thickness of 200 nm was stacked on the first amorphous silicon film. After the second amorphous silicon film is maintained at 300 ° C., the pressure in the chamber is adjusted by an exhaust system so as to be 26.66 Pa (0.2 Torr), and SiH 4 gas is flowed into the chamber from the gas introduction system at a flow rate of 100 sccm, Argon gas flow rate 500sccm,hydrogenEach gas was introduced at 200 sccm, and was formed by plasma CVD while discharging from a high frequency power source at a discharge frequency of 27.12 MHz and an input RF power of 20 W (RF power density 0.033 W / cm 2).
[0031]
Next, the condition of only the input RF power was changed, and a third amorphous silicon film (RF power density 0.166 W / cm) was formed on the second amorphous silicon film.²), Fourth amorphous silicon film (RF power density 0.333 W / cm²), Fifth amorphous silicon film (RF power density 0.5 W / cm²) Were sequentially laminated.
[0032]
The SIMS analysis was performed on the laminated film thus obtained on the semiconductor substrate, the result of measuring the argon concentration in the film is shown in FIG. 2A, the result of measuring the fluorine concentration is shown in FIG. FIG. 3A shows the result of measuring the concentration, and FIG. 3B shows the result of measuring the oxygen concentration. From FIG. 3A, the nitrogen concentration in the film is 1 × 10.¹⁶/ Cm^Three~ 1x10¹⁷/ Cm^ThreeIt can be read as a degree. From FIG. 3B, the oxygen concentration in the film is 4 × 10.¹⁷/ Cm^Three~ 3x10¹⁸/ Cm^ThreeIt can be read as a degree. Although not shown, the carbon concentration in the film is 1 × 10¹⁶/ Cm^Three~ 5x10¹⁷/ Cm^ThreeMet.
[0033]
As apparent from FIGS. 2 and 3, by using hydrogen, argon, and monosilane gas as the source gas, the argon concentration in the amorphous silicon film is 1 × 10.²⁰/ Cm^Three~ 1x10^{twenty one}/ Cm^ThreeIncreased to. Therefore, a high concentration, specifically, 1 × 10 6 is obtained by a plasma CVD method using hydrogen, argon, and monosilane gas as source gases.²⁰/ Cm^Three~ 1x10^{twenty one}/ Cm^ThreeAmorphous silicon film containing argon can be formed at a concentration of 2%. On the other hand, when only monosilane and argon gas are used as the source gas, the argon concentration in the film is 1 × 10¹⁸/ Cm^ThreeBefore and after, ie 5 × 10¹⁷/ Cm^Three~ 2x10¹⁸/ Cm^ThreeIt could only be included.
[0034]
Further, by using hydrogen, argon, and monosilane gas as the source gas, the fluorine concentration in the amorphous silicon film is 2 × 10.¹⁶/ Cm^Three~ 8x10¹⁶/ Cm^ThreeReduced to.
[0035]
Further, as the RF power density was increased, the argon concentration in the amorphous silicon film increased. Even when the RF power density was increased, the fluorine concentration, nitrogen concentration, oxygen concentration, and carbon concentration in the film were hardly changed.
[0036]
(Experiment 2)
Next, plasma CVD was used to vary the pressure conditions in the chamber, and the dependence of the pressure in the chamber on the argon concentration in the amorphous silicon film was examined.
[0037]
First, a first amorphous silicon film serving as a reference was formed on a semiconductor substrate by plasma CVD under the same conditions as in Experiment 1.
[0038]
Next, a second amorphous silicon film having a thickness of 200 nm was stacked on the first amorphous silicon film. After the second amorphous silicon film is maintained at 300 ° C., the pressure in the chamber is adjusted by an exhaust system so as to be 5.332 Pa (0.04 Torr), and SiH is introduced into the chamber from the gas introduction system._FourThe gas was introduced at a flow rate of 100 sccm, the argon gas was introduced at a flow rate of 100 sccm, and the hydrogen gas was introduced at 50 sccm, and the discharge frequency was 27.12 MHz and the input RF power was 20 W (RF power density 0.033 W / cm).²It was formed by plasma CVD while discharging.
[0039]
Next, the conditions of the pressure in the chamber and the gas flow rate are changed, and a third amorphous silicon film (pressure = 4 Pa (0.03 Torr), SiH is formed on the second amorphous silicon film._Four100 sccm for gas, 50 sccm for argon gas, 40 sccm for hydrogen gas, a fourth amorphous silicon film (pressure 2.666 Pa (0.02 Torr), SiH_FourA gas flow rate of 100 sccm, an argon gas flow rate of 15 sccm, and a hydrogen gas of 12 sccm) were sequentially stacked.
[0040]
The SIMS analysis was performed on the laminated film thus obtained on the semiconductor substrate, the result of measuring the argon concentration in the film is shown in FIG. 4A, the result of measuring the fluorine concentration is shown in FIG. FIG. 5A shows the result of measuring the concentration, and FIG. 5B shows the result of measuring the oxygen concentration. The carbon concentration is 1 × 10¹⁶/ Cm^Three~ 5x10^{1 7}/ Cm^ThreeMet.
[0041]
As apparent from FIGS. 4 and 5, the argon concentration in the amorphous silicon film decreased as the pressure was reduced, that is, the vacuum was increased. Even when the pressure was reduced, the fluorine concentration, nitrogen concentration, oxygen concentration, and carbon concentration in the film were hardly changed.
[0042]
(Experiment 3)
Here, the film quality of an amorphous silicon film formed by using plasma CVD and using monosilane, argon element and hydrogen as source gases will be described below.
[0043]
FIG. 16 shows spectral data obtained by Fourier transform infrared spectroscopy (FT-IR method) of an amorphous silicon film formed using monosilane, argon element and hydrogen as source gases. In FIG. 16, a peak of Si—Si bond is observed at a wave number of 640 / cm and a peak is observed at a wave number of 2020 / cm. Wave number 2000 / cm is Si-H bond peak, wave number 2100 / cm is Si-H.₂The peak at a wave number of 2020 / cm in FIG. 16 is mainly a Si—H bond and is slightly Si—H.₂It can be said that it is a peak that appears because it has a bond.
[0044]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
[0045]
(Embodiment 1)
A procedure for manufacturing a typical TFT using the present invention will be briefly described below with reference to FIGS. Here, an example in which a semiconductor film containing a rare gas element of the present invention and having an amorphous structure is used as a gettering site is shown.
[0046]
In FIG. 1A, 10 is a substrate having an insulating surface, 11 is an insulating film to be a blocking layer, and 12 is a semiconductor film having an amorphous structure.
[0047]
In FIG. 1A, a glass substrate, a quartz substrate, a ceramic substrate, or the like can be used as the substrate 10. Alternatively, a silicon substrate, a metal substrate, or a stainless steel substrate with an insulating film formed thereon may be used. Alternatively, a plastic substrate having heat resistance that can withstand the processing temperature in this step may be used.
[0048]
First, as shown in FIG. 1A, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiO_xN_yA base insulating film 11 made of an insulating film is formed. A typical example has a two-layer structure as the base insulating film 11, and SiH_Four, NH_ThreeAnd N₂A first silicon oxynitride film formed using O as a reaction gas is formed in a thickness of 50 to 100 nm, SiH._FourAnd N₂A structure in which a second silicon oxynitride film formed using O as a reaction gas is formed to a thickness of 100 to 150 nm is employed. Further, as a layer of the base insulating film 11, a silicon nitride film (SiN film) having a film thickness of 10 nm or less or a second silicon oxynitride film (SiN)_xO_yIt is preferable to use a film (X >> Y). Since nickel tends to move to a region having a high oxygen concentration during gettering, it is extremely effective to use a silicon nitride film as the base insulating film in contact with the semiconductor film. Alternatively, a three-layer structure in which a first silicon oxynitride film, a second silicon oxynitride film, and a silicon nitride film are sequentially stacked may be used.
[0049]
Next, a first semiconductor film 12 having an amorphous structure is formed over the base insulating film. For the first semiconductor film 12, a semiconductor material containing silicon as a main component is used. Typically, an amorphous silicon film, an amorphous silicon germanium film, or the like is applied, and the film is formed to a thickness of 10 to 100 nm by a plasma CVD method, a low pressure CVD method, or a sputtering method. In order to obtain a semiconductor film having a good crystal structure by subsequent crystallization, the concentration of impurities such as oxygen and nitrogen contained in the film of the first semiconductor film 12 having an amorphous structure is set to 5 × 10.¹⁸/cm^ThreeIt may be reduced to (atomic concentration measured by secondary ion mass spectrometry (SIMS)) or less. These impurities interfere with subsequent crystallization, and also increase the density of capture centers and recombination centers even after crystallization. Therefore, it is desirable not only to use a high-purity material gas but also to use an ultrahigh vacuum-compatible CVD apparatus equipped with a mirror surface treatment (electropolishing treatment) in the reaction chamber and an oil-free vacuum exhaust system.
[0050]
Next, as a technique for crystallizing the first semiconductor film 12 having an amorphous structure, here, the technique described in JP-A-8-78329 is used for crystallization. The technology described in this publication is based on a crystal structure in which an amorphous silicon film (also referred to as an amorphous silicon film) is selectively added with a metal element that promotes crystallization, and heat treatment is performed to expand the added region as a starting point. The semiconductor film which has this is formed. First, on the surface of the first semiconductor film 12 having an amorphous structure, a nickel acetate salt solution containing 1 to 100 ppm in terms of weight of a metal element (here, nickel) having a catalytic action for promoting crystallization is used with a spinner. The nickel-containing layer 13 is formed by coating. (FIG. 1 (B)) As means other than the method for forming the nickel-containing layer 13 by coating, means for forming an extremely thin film by sputtering, vapor deposition, or plasma treatment may be used. Although an example in which the coating is performed on the entire surface is shown here, a nickel-containing layer may be selectively formed by forming a mask.
[0051]
Next, heat treatment is performed to perform crystallization. In this case, in crystallization, silicide is formed in a portion of the semiconductor film in contact with a metal element that promotes crystallization of the semiconductor, and crystallization proceeds using the silicide as a nucleus. Thus, the first semiconductor film 14 having the crystal structure shown in FIG. 1C is formed. Note that the concentration of oxygen contained in the first semiconductor film 14 after crystallization is 5 × 10 5.¹⁸/ Cm^ThreeThe following is desirable. Here, after heat treatment for dehydrogenation (450 ° C., 1 hour), heat treatment for crystallization (550 to 650 ° C. for 4 to 24 hours) is performed. When crystallization is performed by irradiation with strong light, any one of infrared light, visible light, ultraviolet light, or a combination thereof can be used. Typically, a halogen lamp, a metal halide, or the like is used. Light emitted from a lamp, xenon arc lamp, carbon arc lamp, high pressure sodium lamp, or high pressure mercury lamp is used. The lamp light source is turned on for 1 to 60 seconds, preferably 30 to 60 seconds, and this is repeated 1 to 10 times, and the semiconductor film is instantaneously heated to about 600 to 1000 ° C. Note that heat treatment for releasing hydrogen contained in the first semiconductor film 14 having an amorphous structure may be performed before irradiation with strong light, if necessary. In addition, crystallization may be performed by simultaneously performing heat treatment and irradiation with strong light. In consideration of productivity, it is desirable to perform crystallization by irradiation with strong light.
[0052]
The metal element (here, nickel) remains in the first semiconductor film 14 thus obtained. Although it is not uniformly distributed in the film, if it is an average concentration, it is 1 × 10¹⁹/cm^ThreeRemaining at a concentration exceeding Of course, various semiconductor elements including TFT can be formed even in such a state, but the element is removed by the method described below.
[0053]
Next, the first semiconductor film 14 having a crystal structure is irradiated with a laser beam in order to increase the crystallization rate (the ratio of the crystal component in the total volume of the film) and repair defects remaining in the crystal grains. It is preferable. When laser light is irradiated, a thin oxide film (not shown) is formed on the surface. As this laser light, excimer laser light having a wavelength of 400 nm or less, and second harmonic and third harmonic of YAG laser are used. Also, continuous wave laser (YAG laser, YVO_FourLaser, YLF laser, YAlO_ThreeLaser, glass laser, ruby laser, alexandride laser, Ti: sapphire laser) may be used, and the second to fourth harmonics of the fundamental wave may be applied. Typically, Nd: YVO_FourA second harmonic (532 nm) or a third harmonic (355 nm) of a laser (fundamental wave 1064 nm) may be applied. When a continuous wave laser is used, a continuous wave YVO with an output of 10 W is used._FourLaser light emitted from the laser is converted into a harmonic by a non-linear optical element. Also, YVO in the resonator_FourThere is also a method of emitting harmonics by inserting a crystal and a nonlinear optical element. Then, it is preferably formed into a rectangular or elliptical laser beam on the irradiation surface by an optical system, and irradiated to the object to be processed. It is assumed that the shape of the laser beam (laser spot) on the irradiated surface is an elliptical shape having a minor axis length of 3 to 100 μm and a major axis length of 100 μm or more by beam forming means comprising an optical system. Instead of the elliptical shape, a rectangular shape having a short side length of 3 to 100 μm and a long side length of 100 μm or more may be used. The reason why the shape is rectangular or elliptical is to efficiently laser anneal the entire surface of the substrate. Here, the length of the long diameter (or long side) is set to 100 μm or more if the laser beam has an energy density suitable for laser annealing. The practitioner appropriately determines the length of the long diameter (or long side). This is because it only has to be done. The energy density at this time is 0.01 to 100 MW / cm.²Degree (preferably 0.1-10 MW / cm²)is required. Then, irradiation may be performed by moving the semiconductor film relative to the laser light at a speed of about 10 to 2000 cm / s.
[0054]
Since the oxide film formed by the laser light irradiation after crystallization is insufficient, an oxide film (called chemical oxide) is further formed with an aqueous solution containing ozone (typically ozone water). A barrier layer 15 made of an oxide film having a thickness of 1 to 10 nm is formed, and a second semiconductor film 16 containing a rare gas element is formed on the barrier layer 15. Note that, here, an oxide film formed when the first semiconductor film 14 having a crystal structure is irradiated with laser light is also regarded as a part of the barrier layer. This barrier layer 15 functions as an etching stopper when only the second semiconductor film 16 is selectively removed in a later step. Also, chemical oxide can be formed in the same manner by treating with an aqueous solution in which sulfuric acid, hydrochloric acid, nitric acid or the like and hydrogen peroxide are mixed instead of the ozone-containing aqueous solution. Further, as another method for forming the barrier layer 15, the surface of the semiconductor film having the crystal structure may be oxidized by generating ozone by irradiation with ultraviolet rays in an oxygen atmosphere. As another method for forming the barrier layer 15, an oxide film of about 1 to 10 nm may be deposited as a barrier layer by plasma CVD, sputtering, vapor deposition, or the like. When plasma CVD, sputtering, vapor deposition, or the like is used to form the barrier layer, the surface of the semiconductor film having the crystal structure is cleaned, and a natural oxide film or an oxide film formed by laser light irradiation is used. It is desirable to form after removal.
[0055]
Further, when the plasma CVD method is used for forming the barrier layer, a silane-based gas (monosilane, disilane, trisilane, etc.) and a nitrogen oxide-based gas (a gas expressed by NOx) are used as a source gas, and a pulse oscillation is performed. Film. For example, as a source gas, monosilane (SiH_Four) And nitrous oxide (N₂O) or TEOS gas and N₂O or TEOS gas and N₂O and O₂A silicon oxynitride film having a thickness of 10 nm or less, preferably 5 nm or less is formed. This silicon oxynitride film is an oxide film (called chemical oxide) obtained from an ozone-containing aqueous solution (typically ozone water), or a semiconductor film having a crystal structure by generating ozone by irradiation with ultraviolet rays in an oxygen atmosphere. Compared with the oxide film obtained by oxidizing the surface of the film, the adhesion with the first semiconductor film having a crystal structure is high, and peeling does not occur in the subsequent process (formation of the second semiconductor film). In order to further increase the adhesion, an argon plasma treatment may be performed before the barrier layer is formed. In the gettering step, the metal element can pass through the barrier layer and move to the gettering site as long as it is a silicon oxynitride film in the above thickness range.
[0056]
In addition, when the plasma CVD method is used for forming the barrier layer, the second semiconductor film containing a rare gas element and the barrier layer can be formed without being exposed to the atmosphere, and are continuously formed in the same chamber. Therefore, it is possible to form a film, and the throughput is excellent.
[0057]
As another method for forming the barrier layer 15, a thin oxide film may be formed by heating to about 200 to 350 ° C. using a clean oven. Note that the barrier layer 15 formed by any one of the above methods or a combination of these methods has a film quality that allows nickel in the first semiconductor film to move to the second semiconductor film by subsequent gettering. Or it is necessary to set it as a film thickness. In this specification, a barrier layer refers to a layer that has a film quality or a film thickness that allows a metal element to pass in a gettering step and that serves as an etching stopper in a step of removing a layer that becomes a gettering site.
[0058]
Here, the second semiconductor film 16 containing a rare gas element is formed by a plasma CVD method to form a gettering site. As the rare gas element, one or more selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe) are used. Among them, argon (Ar) which is an inexpensive gas is preferable. Here, by using monosilane, argon, or hydrogen as a source gas, argon is 1 × 10 6.¹⁸/ Cm^Three~ 1x10^{twenty two}/ Cm^Three, Preferably 1 × 10²⁰/cm^Three~ 1x10^{twenty one}/cm^ThreeThe second semiconductor film that can be obtained at a concentration and can obtain a gettering effect can be formed by a plasma CVD method. Note that the second semiconductor film has a fluorine concentration of 2 × 10 6 in the film.¹⁶/ Cm^Three~ 8x10¹⁶/ Cm^ThreeThe concentration of hydrogen is reduced to a relatively low value.
[0059]
There are two meanings of including a rare gas element ion which is an inert gas in the film. One is to form a dangling bond to give distortion to the semiconductor film, and the other is to give distortion to the lattice of the semiconductor film. Distortion between the lattices of the semiconductor film can be obtained remarkably when an element having an atomic radius larger than that of silicon such as argon (Ar), krypton (Kr), or xenon (Xe) is used. Further, by containing a rare gas element in the film, not only lattice distortion but also dangling bonds are formed, contributing to the gettering action.
[0060]
Next, heat treatment is performed, and gettering for reducing or removing the concentration of the metal element (nickel) in the first semiconductor film is performed. (FIG. 1E) Heat treatment for performing gettering may be performed by irradiation with intense light or heat treatment. By this gettering, the metal element moves in the direction of the arrow in FIG. 1E (that is, the direction from the substrate side to the surface of the second semiconductor film), and the first semiconductor film covered with the barrier layer 15 14 is removed or the concentration of the metal element is reduced. The distance that the metal element travels during gettering may be at least as long as the thickness of the first semiconductor film, and the gettering can be completed in a relatively short time. Here, all the nickel is moved to the second semiconductor film 16 so as not to segregate to the first semiconductor film 16, and the nickel contained in the first semiconductor film 14 is hardly present, that is, the nickel concentration in the film is 1 ×. 10¹⁸/ Cm^ThreeBelow, desirably 1 × 10¹⁷/ Cm^ThreeGetter enough to get:
[0061]
Note that the second semiconductor film may be partially crystallized depending on the conditions of the heat treatment for the gettering or the thickness of the second semiconductor film. If the second semiconductor film is crystallized, dangling bonds, lattice distortion, and dangling bonds are reduced, and the gettering effect is reduced. Therefore, it is preferable that the second semiconductor film is not crystallized. Or the thickness of the second semiconductor film. In any case, the second semiconductor film, that is, an amorphous silicon film containing a rare gas element, is less likely to be crystallized than an amorphous silicon film containing no rare gas element, so that it is optimal as a gettering site. It is.
[0062]
Depending on the conditions of the heat treatment for the gettering, the crystallization rate of the first semiconductor film can be increased at the same time as the gettering, and defects remaining in the crystal grains can be repaired, that is, the crystallinity can be improved. .
[0063]
In this specification, gettering means that a metal element in a gettering region (here, the first semiconductor film) is released by thermal energy and moves to a gettering site by diffusion. Accordingly, the gettering depends on the processing temperature, and the gettering proceeds in a shorter time as the temperature is higher.
[0064]
When using the process of irradiating intense light, the lamp light source for heating is turned on for 1 to 60 seconds, preferably 30 to 60 seconds, and this is repeated 1 to 10 times, preferably 2 to 6 times. The emission intensity of the lamp light source is arbitrary, but the semiconductor film is instantaneously heated to 600 to 1000 ° C., preferably about 700 to 750 ° C.
[0065]
In the case where the heat treatment is performed, the heat treatment may be performed in a nitrogen atmosphere at 450 to 800 ° C. for 1 to 24 hours, for example, at 550 ° C. for 14 hours. Moreover, you may irradiate strong light in addition to heat processing.
[0066]
Next, using the barrier layer 15 as an etching stopper, only the second semiconductor film indicated by 16 is selectively removed, and then the barrier layer 15 is removed and the first semiconductor film 16 is desired using a known patterning technique. The semiconductor layer 17 having the shape is formed. (FIG. 1F) As a method of selectively etching only the second semiconductor film, ClF_ThreeDry etching without plasma by hydrazine, tetraethylammonium hydroxide (chemical formula (CH_Three)_FourNOH) can be performed by wet etching with an alkaline solution such as an aqueous solution. Further, after removing the second semiconductor film, the nickel concentration was measured on the surface of the barrier layer by TXRF. As nickel was detected at a high concentration, it is desirable to remove the barrier layer, and an etchant containing hydrofluoric acid. It may be removed by Further, it is desirable to form a thin oxide film on the surface with ozone water after removing the barrier layer and before forming a resist mask.
[0067]
Next, after cleaning the surface of the semiconductor layer with an etchant containing hydrofluoric acid, an insulating film containing silicon as a main component and serving as the gate insulating film 18 is formed. The surface cleaning and the formation of the gate insulating film are desirably performed continuously without exposure to the atmosphere.
[0068]
Next, after cleaning the surface of the gate insulating film 18, a gate electrode 19 is formed. Next, an impurity element imparting n-type conductivity to the semiconductor (P, As, or the like), here, phosphorus is added as appropriate, so that the source region 20 and the drain region 21 are formed. After the addition, heat treatment, intense light irradiation, or laser light irradiation is performed to activate the impurity element. Simultaneously with activation, plasma damage to the gate insulating film and plasma damage to the interface between the gate insulating film and the semiconductor layer can be recovered. In particular, in an atmosphere of room temperature to 300 ° C., it is very effective to activate the impurity element by irradiating the second harmonic of the YAG laser from the front surface or the back surface. A YAG laser is a preferred activation means because it requires less maintenance.
[0069]
In the subsequent steps, an interlayer insulating film 23 is formed, hydrogenation is performed, contact holes reaching the source region and the drain region are formed, a source electrode 24 and a drain electrode 25 are formed, and a TFT (n-channel TFT) To complete. (Fig. 1 (G))
[0070]
The concentration of the metal element contained in the channel formation region 22 of the TFT thus obtained is 1 × 10¹⁷/ Cm^ThreeLess than.
[0071]
Further, the present invention is not limited to the TFT structure of FIG. 1G, and if necessary, a lightly doped drain (LDD) having an LDD region between a channel formation region and a drain region (or source region). ) Structure may be used. In this structure, a region to which an impurity element is added at a low concentration is provided between a channel formation region and a source region or a drain region formed by adding an impurity element at a high concentration, and this region is referred to as an LDD region. I'm calling. Further, a so-called GOLD (Gate-drain Overlapped LDD) structure in which an LDD region is disposed so as to overlap with a gate electrode through a gate insulating film may be employed.
[0072]
Although an n-channel TFT has been described here, it goes without saying that a p-channel TFT can be formed by using a p-type impurity element instead of an n-type impurity element.
[0073]
Although the top gate type TFT has been described as an example here, the present invention can be applied regardless of the TFT structure. For example, it can be applied to a bottom gate type (reverse stagger type) TFT or a forward stagger type TFT. Is possible.
[0074]
(Embodiment 2)
Here, an example in which a semiconductor film containing a rare gas element of the present invention and having an amorphous structure is used as an active layer of a TFT is shown.
[0075]
First, a gate electrode is formed over a substrate having an insulating surface, a gate insulating film covering the gate electrode is formed, and the gate insulating film contains the rare gas element of the present invention and has an amorphous structure. A first semiconductor film is formed. Here, by using monosilane, argon, or hydrogen as a source gas, argon is 1 × 10 6.¹⁸/ Cm^Three~ 1x10^{twenty two}/ Cm^Three, Preferably 1 × 10²⁰/cm^Three~ 1x10^{twenty one}/cm^ThreeAnd 2 × 10 fluorine.¹⁶/ Cm^Three~ 8x10¹⁶/ Cm^ThreeAnd a first semiconductor film having an amorphous structure with a relatively low hydrogen concentration can be formed by a plasma CVD method. Next, a second semiconductor film containing an impurity element of one conductivity type (n-type or p-type) is stacked. Next, unnecessary portions of the first semiconductor film having an amorphous structure other than the portion serving as the active layer are removed by etching. Next, after a conductive film made of a conductive film is formed over the entire surface, a part of the conductive film and the second semiconductor film containing an impurity element of one conductivity type (n-type or p-type) is removed, and the semiconductor A source region and a drain region made of a film are formed, and simultaneously, a drain wiring and a source wiring made of a conductive film are also formed. Further, a part of the first semiconductor film is removed, and a channel-etch type bottom gate TFT is manufactured. If a pixel electrode is provided in this TFT, it can be used for a TFT in a pixel portion in a liquid crystal display device.
[0076]
Further, the present invention is not limited to the above-described TFT called an amorphous silicon TFT, but can also be applied to an active layer of a TFT called a polysilicon TFT.
[0077]
In that case, as the first semiconductor film 12 having an amorphous structure provided over the base insulating film described in Embodiment Mode 1, the first semiconductor containing the rare gas element of the present invention and having an amorphous structure is used. Use a membrane. Then, crystallization is performed by a crystallization technique (solid phase growth method, laser crystallization method, solid phase growth method by heat treatment using a metal element as a catalyst) to form a semiconductor having a crystal structure, and patterning is performed to obtain a TFT. The active layer may be used. The semiconductor film having an amorphous structure of the present invention is advantageous in crystallization because the hydrogen concentration and fluorine concentration in the film are reduced. Here, by using monosilane, argon, or hydrogen as a source gas, argon is 1 × 10 6.¹⁸/ Cm^Three~ 1x10^{twenty two}/ Cm^Three, Preferably 1 × 10²⁰/cm^Three~ 1x10^{twenty one}/cm^ThreeThe first semiconductor film having the amorphous structure and having an amorphous structure can be formed by a plasma CVD method.
[0078]
For example, in the case of performing laser crystallization, after forming a first semiconductor film containing a rare gas element and nitrogen of the present invention and having an amorphous structure over a substrate having an insulating surface, laser crystallization is performed. Do.
[0079]
  As the laser light to be used, excimer laser, YAG laser, YVO, which are pulse oscillation type or continuous emission type, are used._FourLaser, YLF laser, YAlO_ThreeLaser, glass laser, ruby laser, alexander dryGA laser, a Ti: sapphire laser, or the like can be used. When these lasers are used, it is preferable to use a method in which laser light emitted from a laser oscillator is linearly collected by an optical system and irradiated onto a semiconductor film. The conditions for crystallization are appropriately selected by the practitioner. When a pulsed excimer laser is used, the pulse oscillation frequency is 30 Hz, and the laser energy density is 100 to 400 mJ / cm.²(Typically 200-300mJ / cm²). Also, pulse oscillation type YAG laser and YVO_FourWhen using a laser, the second harmonic or the third harmonic is used and the pulse oscillation frequency is 1 to 10 kHz, and the laser energy density is 300 to 600 mJ / cm.²(Typically 350-500mJ / cm²) Then, when the laser beam condensed linearly with a width of 100 to 1000 μm, for example 400 μm, is irradiated over the entire surface of the substrate, the superposition ratio (overlap ratio) of the linear laser light at this time is 80 to 98%. Good.
[0080]
YVO_FourWhen a continuous wave laser represented by a laser is used, a continuous wave YVO with an output of 10 W is used._FourLaser light emitted from the laser is converted into a harmonic (second harmonic to fourth harmonic) by a nonlinear optical element. Also, YVO in the resonator_FourThere is also a method of emitting harmonics by inserting a crystal and a nonlinear optical element. Then, it is preferably formed into a rectangular or elliptical laser beam on the irradiation surface by an optical system, and irradiated to the object to be processed. The energy density at this time is 0.01 to 100 MW / cm.²Degree (preferably 0.1-10 MW / cm²)is required. Then, irradiation may be performed by moving the semiconductor film relative to the laser light at a speed of about 0.5 to 2000 cm / s.
[0081]
(Embodiment 3)
In addition, the semiconductor film containing a rare gas element and having an amorphous structure according to the present invention is formed by etching treatment or laser beam when separating the substrate and the element such as TFT after forming each element on the substrate. It can also be used as a layer (peeling layer) in which a peeling phenomenon occurs in the layer or at the interface by irradiation. This release layer is provided in contact with the substrate, and an insulating film and a TFT are formed on the release layer.
[0082]
In addition, a semiconductor film containing a rare gas element and having an amorphous structure according to the present invention has an etching rate different from that of a conventional semiconductor film having an amorphous structure, so that it is used as an etching stopper in various etching processes. Can be used.
[0083]
Further, the semiconductor film containing the rare gas element of the present invention and having an amorphous structure includes a semiconductor film crystallized by a method different from the method described in Embodiment 1, and other general semiconductors. It can also be used as a film gettering site.
[0084]
The present invention having the above-described configuration will be described in more detail with the following examples.
[0085]
(Example)
[Example 1]
An embodiment of the present invention will be described with reference to FIGS. Here, a method for simultaneously manufacturing a pixel portion and TFTs (n-channel TFT and p-channel TFT) of a driver circuit provided around the pixel portion on the same substrate will be described in detail.
[0086]
First, a base insulating film 101 is formed over a substrate 100 to obtain a first semiconductor film having a crystal structure, and then etching processing into a desired shape is performed to form semiconductor layers 102 to 106 separated into island shapes. .
[0087]
As the substrate 100, a glass substrate (# 1737) is used, and as the base insulating film 101, a film formation temperature of 400 ° C. and a source gas SiH are formed by plasma CVD._Four, NH_Three, N₂A silicon oxynitride film 101a made of O (composition ratio Si = 32%, O = 27%, N = 24%, H = 17%) is formed to 50 nm (preferably 10 to 200 nm). Next, after cleaning the surface with ozone water, the oxide film on the surface is removed with dilute hydrofluoric acid (1/100 dilution). Next, the film formation temperature is 400 ° C. by the plasma CVD method, and the source gas SiH._Four, N₂A silicon oxynitride film 101b made of O (composition ratio Si = 32%, O = 59%, N = 7%, H = 2%) is laminated to a thickness of 100 nm (preferably 50 to 200 nm), Furthermore, the film deposition temperature is 300 ° C. and the film deposition gas SiH is formed by plasma CVD without opening to the atmosphere._FourA semiconductor film having an amorphous structure (here, an amorphous silicon film) is formed with a thickness of 54 nm (preferably 25 to 80 nm).
[0088]
Although the base film 101 is shown as a two-layer structure in this embodiment, it may be formed as a single layer film of the insulating film or a structure in which two or more layers are stacked. The material of the semiconductor film is not limited, but preferably silicon or silicon germanium (Si_1-XGe_X(X = 0.0001 to 0.02)) An alloy or the like may be used and may be formed by a known means (such as sputtering, LPCVD, or plasma CVD). The plasma CVD apparatus may be a single wafer type apparatus or a batch type apparatus. Alternatively, the base insulating film and the semiconductor film may be successively formed without being exposed to the air in the same film formation chamber.
[0089]
Next, after cleaning the surface of the semiconductor film having an amorphous structure, an extremely thin oxide film of about 2 nm is formed on the surface with ozone water. Next, a small amount of impurity element (boron or phosphorus) is doped in order to control the threshold value of the TFT. Here, diborane (B₂H₆) Using a plasma-excited ion doping method without mass separation, a doping condition of an acceleration voltage of 15 kV, diborane diluted to 1% with hydrogen, a gas flow rate of 30 sccm, a dose of 2 × 10¹²/ Cm²Then, boron was added to the amorphous silicon film.
[0090]
Next, a nickel acetate salt solution containing 10 ppm of nickel by weight is applied by a spinner. Instead of coating, a method of spreading nickel element over the entire surface by sputtering may be used.
[0091]
Next, heat treatment is performed for crystallization, so that a semiconductor film having a crystal structure is formed. For this heat treatment, heat treatment in an electric furnace or irradiation with strong light may be used. When the heat treatment is performed in an electric furnace, the heat treatment may be performed at 500 ° C. to 650 ° C. for 4 to 24 hours. Here, after heat treatment for dehydrogenation (500 ° C., 1 hour), heat treatment for crystallization (550 ° C., 4 hours) is performed to obtain a silicon film having a crystal structure. Note that although crystallization is performed here using heat treatment using a furnace, crystallization may be performed using a lamp annealing apparatus. Although a crystallization technique using nickel as a metal element for promoting crystallization of silicon is used here, other known crystallization techniques such as a solid phase growth method and a laser crystallization method may be used.
[0092]
Next, after removing the oxide film on the surface of the silicon film having a crystal structure with dilute hydrofluoric acid or the like, a first laser beam (XeCl: wavelength 308 nm) for increasing the crystallization rate and repairing defects left in the crystal grains ) Is performed in the air or in an oxygen atmosphere. As the laser light, excimer laser light having a wavelength of 400 nm or less, and second harmonic and third harmonic of a YAG laser are used. In any case, a pulse laser beam having a repetition frequency of about 10 to 1000 Hz is used, and the laser beam is 100 to 500 mJ / cm in an optical system.²And the surface of the silicon film may be scanned by irradiating with an overlap rate of 90 to 95%. Here, repetition frequency 30Hz, energy density 393mJ / cm²Then, the first laser beam is irradiated in the atmosphere. Note that an oxide film is formed on the surface by irradiation with the first laser light because it is performed in the air or in an oxygen atmosphere.
[0093]
Next, after removing the oxide film formed by irradiation with the first laser beam with dilute hydrofluoric acid, irradiation with the second laser beam is performed in a nitrogen atmosphere or in a vacuum to flatten the surface of the semiconductor film. As this laser light (second laser light), excimer laser light having a wavelength of 400 nm or less, and second and third harmonics of a YAG laser are used. The energy density of the second laser beam is larger than the energy density of the first laser beam, preferably 30 to 60 mJ / cm.²Enlarge. Here, repetition frequency 30Hz, energy density 453mJ / cm²Then, the second laser beam is irradiated, and the PV value (Peak to Valley, difference between the maximum value and the minimum value) of the unevenness on the surface of the semiconductor film becomes 50 nm or less. This PV value is obtained by an AFM (atomic force microscope).
[0094]
In this embodiment, the second laser beam is irradiated on the entire surface. However, since the reduction of the off-current is particularly effective for the TFT in the pixel portion, it is possible to selectively irradiate at least the pixel portion. Good.
[0095]
Further, in this embodiment, the example in which the second laser light is irradiated and planarized is shown, but this need not be particularly performed.
[0096]
Next, the surface is treated with ozone water for 120 seconds to form a barrier layer made of an oxide film having a total thickness of 1 to 5 nm.
[0097]
Next, an amorphous silicon film containing an argon element serving as a gettering site is formed with a thickness of 150 nm over the barrier layer by the plasma CVD method described in Embodiment Mode 1.
[0098]
The film forming conditions by the plasma CVD method of this embodiment are that the substrate temperature is 300 ° C., the pressure in the chamber is 26.66 Pa (0.2 Torr), and SiH is introduced into the chamber from the gas introduction system._FourGas was introduced at a flow rate of 100 sccm, argon gas was introduced at a flow rate of 500 sccm, and hydrogen gas was introduced at a rate of 200 sccm.²). Note that the atomic concentration of the argon element contained in the amorphous silicon film under the above conditions is 1 × 10²⁰/ Cm^Three~ 1x10^{twenty one}/ Cm^ThreeIt is. Thereafter, heat treatment is performed at 650 ° C. for 3 minutes using a lamp annealing apparatus to perform gettering.
[0099]
Next, the amorphous silicon film containing an argon element as a gettering site is selectively removed using the barrier layer as an etching stopper, and then the barrier layer is selectively removed with dilute hydrofluoric acid. Note that during gettering, nickel tends to move to a region with a high oxygen concentration, and thus it is desirable to remove the barrier layer made of an oxide film after gettering.
[0100]
Next, after forming a thin oxide film with ozone water on the surface of the obtained silicon film having a crystal structure (also called a polysilicon film), a mask made of resist is formed and etched into a desired shape to form islands. The separated semiconductor layers 102 to 106 are formed. After the semiconductor layer is formed, the resist mask is removed.
[0101]
Next, the oxide film is removed with an etchant containing hydrofluoric acid, and at the same time, the surface of the silicon film is washed, and then an insulating film containing silicon as a main component to be the gate insulating film 107 is formed. In this embodiment, a silicon oxynitride film (composition ratio: Si = 32%, O = 59%, N = 7%, H = 2%) is formed to a thickness of 115 nm by plasma CVD.
[0102]
Next, as illustrated in FIG. 6A, a first conductive film 108 a with a thickness of 20 to 100 nm and a second conductive film 108 b with a thickness of 100 to 400 nm are stacked over the gate insulating film 107. In this embodiment, a tantalum nitride film with a thickness of 50 nm and a tungsten film with a thickness of 370 nm are sequentially stacked on the gate insulating film 107.
[0103]
The conductive material for forming the first conductive film and the second conductive film is an element selected from Ta, W, Ti, Mo, Al, and Cu, or an alloy material or a compound material containing the element as a main component. Form. Alternatively, a semiconductor film typified by a polycrystalline silicon film doped with an impurity element such as phosphorus, or an AgPdCu alloy may be used as the first conductive film and the second conductive film. Further, the present invention is not limited to the two-layer structure. For example, a three-layer structure in which a 50 nm-thickness tungsten film, a 500 nm-thickness aluminum and silicon alloy (Al-Si) film, and a 30 nm-thickness titanium nitride film are sequentially stacked. Also good. In the case of a three-layer structure, tungsten nitride may be used instead of tungsten of the first conductive film, or aluminum instead of the aluminum and silicon alloy (Al-Si) film of the second conductive film. A titanium alloy film (Al—Ti) may be used, or a titanium film may be used instead of the titanium nitride film of the third conductive film. Moreover, a single layer structure may be sufficient.
[0104]
Next, as shown in FIG. 6B, masks 110 to 115 made of resist are formed by a light exposure process, and a first etching process for forming gate electrodes and wirings is performed. The first etching process is performed under the first and second etching conditions. For etching, an ICP (Inductively Coupled Plasma) etching method may be used. Using the ICP etching method, the film is formed into a desired taper shape by appropriately adjusting the etching conditions (the amount of power applied to the coil-type electrode, the amount of power applied to the substrate-side electrode, the electrode temperature on the substrate side, etc.) Can be etched. As an etching gas, Cl₂, BCl_Three, SiCl_Four, CCl_FourChlorine gas or CF represented by_Four, SF₆, NF_ThreeFluorine gas such as O₂Can be used as appropriate.
[0105]
In this embodiment, 150 W RF (13.56 MHz) power is also applied to the substrate side (sample stage), and a substantially negative self-bias voltage is applied. The electrode area size on the substrate side is 12.5 cm × 12.5 cm, and the coil-type electrode area size (here, the quartz disk provided with the coil) is a disk having a diameter of 25 cm. The W film is etched under this first etching condition so that the end portion of the first conductive layer is tapered. Under the first etching conditions, the etching rate with respect to W is 200.39 nm / min, the etching rate with respect to TaN is 80.32 nm / min, and the selection ratio of W with respect to TaN is about 2.5. Further, the taper angle of W is about 26 ° under this first etching condition. Thereafter, the resist masks 110 to 115 are not removed and the second etching condition is changed, and the etching gas is changed to CF._FourAnd Cl₂The gas flow ratio is 30/30 (sccm), and 500 W of RF (13.56 MHz) power is applied to the coil-type electrode at a pressure of 1 Pa to generate plasma and etching for about 30 seconds. Went. 20 W of RF (13.56 MHz) power is also applied to the substrate side (sample stage), and a substantially negative self-bias voltage is applied. CF_FourAnd Cl₂Under the second etching condition in which is mixed, the W film and the TaN film are etched to the same extent. The etching rate for W under the second etching conditions is 58.97 nm / min, and the etching rate for TaN is 66.43 nm / min. Note that in order to perform etching without leaving a residue on the gate insulating film, it is preferable to increase the etching time at a rate of about 10 to 20%.
[0106]
In the first etching process, the shape of the mask made of resist is made suitable, and the end portions of the first conductive layer and the second conductive layer are tapered due to the effect of the bias voltage applied to the substrate side. It becomes. The angle of the tapered portion may be 15 to 45 °.
[0107]
Thus, first-shaped conductive layers 117 to 121 (first conductive layers 117 a to 121 a and second conductive layers 117 b to 121 b) composed of the first conductive layer and the second conductive layer by the first etching process. Form. The insulating film 107 to be a gate insulating film is etched by about 10 to 20 nm to become a gate insulating film 116 in which a region not covered with the first shape conductive layers 117 to 121 is thinned.
[0108]
Next, a second etching process is performed without removing the resist mask. (FIG. 6C) Here, SF is used as the etching gas.₆And Cl₂And O₂The gas flow ratio is 24/12/24 (sccm), and 700 W of RF (13.56 MHz) power is applied to the coil-type electrode at a pressure of 1.3 Pa to generate plasma and perform etching. 25 seconds. 10 W RF (13.56 MHz) power is also applied to the substrate side (sample stage), and a substantially negative self-bias voltage is applied. In the second etching process, the etching rate with respect to W is 227.3 nm / min, the etching rate with respect to TaN is 32.1 nm / min, the selection ratio of W with respect to TaN is 7.1, and the SiON that is the insulating film 116 The etching rate with respect to is 33.7 nm / min, and the selective ratio of W to SiON is 6.83. In this way, SF is used as the etching gas.₆Is used, the selectivity with respect to the insulating film 116 is high, so that film loss can be suppressed. In this embodiment, the insulating film 116 is reduced only by about 8 nm.
[0109]
By this second etching process, the taper angle of W became 70 °. The second conductive layers 124b to 129b are formed by the second etching process. On the other hand, the first conductive layer is hardly etched and becomes the first conductive layers 124a to 129a. Note that the first conductive layers 124a to 129a are approximately the same size as the first conductive layers 117a to 122a. Actually, the width of the first conductive layer may be about 0.3 μm, that is, the entire line width may be receded by about 0.6 μm as compared with that before the second etching process, but the size is hardly changed. In FIGS. 6B and 6C, the length of the tapered portion of the first conductive layer is shown to be the same. However, since there is actually a dependency on the wiring width, the first conductive layer depends on the wiring width. The length of the taper portion of one conductive layer changes.
[0110]
In place of the two-layer structure, a three-layer structure in which a 50-nm-thick tungsten film, a 500-nm-thick aluminum and silicon alloy (Al-Si) film, and a 30-nm-thick titanium nitride film are sequentially stacked, As the first etching condition of the first etching process, BCl_ThreeAnd Cl₂And O₂Are used as source gases, each gas flow rate ratio is 65/10/5 (sccm), 300 W RF (13.56 MHz) power is applied to the substrate side (sample stage), and the coil is operated at a pressure of 1.2 Pa. 450 W RF (13.56 MHz) power is applied to the electrode of the mold to generate plasma and perform etching for 117 seconds. The second etching condition of the first etching process is CF_FourAnd Cl₂And O₂Each gas flow rate ratio is 25/25/10 (sccm), 20 W RF (13.56 MHz) power is supplied to the substrate side (sample stage), and a coil type electrode is applied at a pressure of 1 Pa. An RF (13.56 MHz) power of 500 W is applied to generate plasma, and etching may be performed for about 30 seconds. As the second etching process, BCl is used._ThreeAnd Cl₂Each gas flow rate ratio is 20/60 (sccm), 100 W RF (13.56 MHz) power is supplied to the substrate side (sample stage), and 600 W is applied to the coil-type electrode at a pressure of 1.2 Pa. RF (13.56 MHz) power may be input to generate plasma and perform etching.
[0111]
Next, after removing the resist mask, a first doping process is performed to obtain the state of FIG. The doping process may be performed by ion doping or ion implantation. The condition of the ion doping method is that the dose is 1.5 × 10¹⁴atoms / cm²The acceleration voltage is set to 60 to 100 keV. Typically, phosphorus (P) or arsenic (As) is used as the impurity element imparting n-type conductivity. In this case, the first conductive layer and the second conductive layers 124 to 128 serve as a mask for the impurity element imparting n-type, and the first impurity regions 130 to 134 are formed in a self-aligning manner. The first impurity regions 130 to 134 have 1 × 10¹⁶~ 1x10¹⁷/cm^ThreeAn impurity element imparting n-type is added in a concentration range of. Here, a region having the same concentration range as the first impurity region is n^-Also called a region.
[0112]
In this embodiment, the first doping process is performed after removing the resist mask, but the first doping process may be performed without removing the resist mask. In FIG. 6D, for the sake of convenience, the length of the tapered portion of the first conductive layer is illustrated as being the same, but actually, the length of the tapered portion of the first conductive layer varies depending on the wiring width. ing. Therefore, when a plurality of wirings having different wiring widths are provided on the same substrate, the widths of the doped regions are also different.
[0113]
Next, as shown in FIG. 7A, masks 135 to 137 made of resist are formed, and a second doping process is performed. The mask 135 is a mask that protects the channel formation region of the semiconductor layer that forms the p-channel TFT of the driver circuit and its peripheral region, and the mask 136 is a semiconductor layer that forms one of the n-channel TFTs of the driver circuit. The mask 137 is a mask for protecting the channel formation region and its peripheral region, and the mask 137 is a mask for protecting the channel formation region of the semiconductor layer forming the TFT of the pixel portion, its peripheral region, and the region serving as a storage capacitor.
[0114]
The condition of the ion doping method in the second doping process is that the dose is 1.5 × 10 5.¹⁵atoms / cm²Then, phosphorus (P) is doped with an acceleration voltage of 60 to 100 keV. Here, impurity regions are formed in each semiconductor layer in a self-aligned manner using the second conductive layers 124b to 126b as masks. Of course, it is not added to the region covered with the masks 135 to 137. Thus, the second impurity regions 138 to 140 and the third impurity region 142 are formed. The second impurity regions 138 to 140 have 1 × 10²⁰~ 1x10^{twenty one}/cm^ThreeAn impurity element imparting n-type is added in a concentration range of. Here, a region having the same concentration range as the second impurity region is n⁺Also called a region.
[0115]
The third impurity region is formed at a lower concentration than the second impurity region by the first conductive layer, and is 1 × 10 6.¹⁸~ 1x10¹⁹/cm^ThreeAn impurity element imparting n-type is added in a concentration range of. Note that the third impurity region has a concentration gradient in which the impurity concentration increases toward the end portion of the tapered portion because doping is performed by passing the portion of the first conductive layer having a tapered shape. . Here, a region having the same concentration range as the third impurity region is n^-Also called a region. The regions covered with the masks 136 and 137 become the first impurity regions 144 and 145 to which no impurity element is added in the second doping process.
[0116]
Next, after removing the resist masks 135 to 137, new resist masks 146 to 148 are formed, and a third doping process is performed as shown in FIG. 7B.
[0117]
In the driver circuit, a fourth impurity region 149 in which an impurity element imparting p-type conductivity is added to the semiconductor layer forming the p-channel TFT and the semiconductor layer forming the storage capacitor by the third doping process. 150 and fifth impurity regions 151 and 152 are formed.
[0118]
The fourth impurity regions 149 and 150 have 1 × 10 6.²⁰~ 1x10^{twenty one}/cm^ThreeAn impurity element imparting p-type is added in a concentration range of. Note that the fourth impurity regions 149 and 150 are regions (n) to which phosphorus (P) is added in the previous step.^-The concentration of the impurity element imparting p-type is 1.5 to 3 times that of the impurity element, and the conductivity type is p-type. Here, a region having the same concentration range as the fourth impurity region is represented by p.⁺Also called a region.
[0119]
The fifth impurity regions 151 and 152 are formed in a region overlapping with the tapered portion of the second conductive layer 125a, and 1 × 10¹⁸~ 1x10²⁰/cm^ThreeAn impurity element imparting p-type is added in a concentration range of. Here, a region having the same concentration range as the fifth impurity region is represented by p.^-Also called a region.
[0120]
Through the above steps, impurity regions having n-type or p-type conductivity are formed in each semiconductor layer. The conductive layers 124 to 127 serve as TFT gate electrodes. The conductive layer 128 serves as one electrode forming a storage capacitor in the pixel portion. Further, the conductive layer 129 forms a source wiring in the pixel portion.
[0121]
In addition, as long as the conductive layers 124 to 127 and the impurity regions (first impurity region to fifth impurity region) can be formed, the process order is not particularly limited, and each etching order and each doping order are changed as appropriate. Also good.
[0122]
Next, an insulating film (not shown) that covers substantially the entire surface is formed. In this example, a 50 nm-thickness silicon oxide film was formed by plasma CVD. Of course, this insulating film is not limited to the silicon oxide film, and another insulating film containing silicon may be used as a single layer or a laminated structure.
[0123]
Next, a step of activating the impurity element added to each semiconductor layer is performed. This activation process is performed by a rapid thermal annealing method (RTA method) using a lamp light source, a method of irradiating a YAG laser or an excimer laser from the back surface, a heat treatment using a furnace, or a combination thereof. By different methods.
[0124]
Further, in this embodiment, an example in which an insulating film is formed before the activation is shown, but an insulating film may be formed after the activation.
[0125]
Next, a first interlayer insulating film 153 made of a silicon nitride film is formed and subjected to a heat treatment (heat treatment at 300 to 550 ° C. for 1 to 12 hours) to hydrogenate the semiconductor layer. (FIG. 7C) This step is a step of terminating dangling bonds in the semiconductor layer with hydrogen contained in the first interlayer insulating film 153. The semiconductor layer can be hydrogenated regardless of the presence of an insulating film (not shown) made of a silicon oxide film. However, in this embodiment, since the material containing aluminum as a main component is used as the second conductive layer, it is important to set the heat treatment conditions that the second conductive layer can withstand in the hydrogenation step. As another means of hydrogenation, plasma hydrogenation (using hydrogen excited by plasma) may be performed.
[0126]
Next, a second interlayer insulating film 154 made of an organic insulating material is formed on the first interlayer insulating film 153. In this embodiment, an acrylic resin film having a thickness of 1.6 μm is formed. Next, a contact hole reaching the source wiring 129, a contact hole reaching the conductive layers 127 and 128, and a contact hole reaching each impurity region are formed. In this embodiment, a plurality of etching processes are sequentially performed. In this embodiment, after etching the second interlayer insulating film using the first interlayer insulating film as an etching stopper, the first interlayer insulating film is etched using the insulating film (not shown) as an etching stopper, and then the insulating film (illustrated). Not etched).
[0127]
Thereafter, wirings and pixel electrodes are formed using Al, Ti, Mo, W, or the like. As the material of these electrodes and pixel electrodes, it is desirable to use a material having excellent reflectivity such as a film mainly composed of Al or Ag, or a laminated film thereof. Thus, the source or drain electrodes 155 to 160, the gate wiring 162, the connection wiring 161, and the pixel electrode 163 are formed.
[0128]
As described above, the pixel portion 207 including the driving circuit 206 including the n-channel TFT 201, the p-channel TFT 202, and the n-channel TFT 203, the pixel TFT 204 including the n-channel TFT, and the storage capacitor 205 is formed over the same substrate. Can be formed. (FIG. 8) In this specification, such a substrate is referred to as an active matrix substrate for convenience. In this specification, such a substrate is referred to as an active matrix substrate for convenience.
[0129]
In the pixel portion 207, the pixel TFT 204 (n-channel TFT) includes a channel formation region 167 and a first impurity region (n formed outside the conductive layer 127 forming the gate electrode).^-Region) 145 and a second impurity region (n⁺Region) 140. A fourth impurity region 150 and a fifth impurity region 152 are formed in the semiconductor layer functioning as one electrode of the storage capacitor 205. The storage capacitor 205 is formed of the second electrode 128 and the semiconductor layers 150, 152, and 168 using the insulating film (same film as the gate insulating film) 116 as a dielectric.
[0130]
In the driver circuit 206, the n-channel TFT 201 (first n-channel TFT) includes a third impurity region (a first n-channel TFT) that overlaps with the channel formation region 164 and part of the conductive layer 124 forming the gate electrode with an insulating film interposed therebetween. n^-Region) 142 and a second impurity region (n that functions as a source region or a drain region)⁺Region) 138.
[0131]
In the driver circuit 206, the p-channel TFT 202 includes a channel formation region 165 and a fifth impurity region (p) overlapping with a part of the conductive layer 125 forming the gate electrode through an insulating film.^-Region) 151 and a fourth impurity region (p) functioning as a source region or a drain region⁺Region) 149.
[0132]
In the driver circuit 206, the n-channel TFT 203 (second n-channel TFT) has a channel formation region 166 and a first impurity region (n on the outside of the conductive layer 126 for forming a gate electrode).^-Region) 144 and a second impurity region (n that functions as a source region or a drain region)⁺Region) 139.
[0133]
A driving circuit 206 may be formed by appropriately combining these TFTs 201 to 203 to form a shift register circuit, a buffer circuit, a level shifter circuit, a latch circuit, and the like. For example, in the case of forming a CMOS circuit, an n-channel TFT 201 and a p-channel TFT 202 may be complementarily connected.
[0134]
In particular, the structure of the n-channel TFT 203 is suitable for a buffer circuit having a high driving voltage in order to prevent deterioration due to the hot carrier effect.
[0135]
In addition, the structure of the n-channel TFT 201 having a GOLD structure is suitable for a circuit in which reliability is given the highest priority.
[0136]
In addition, since the reliability can be improved by improving the planarization of the surface of the semiconductor film, it is sufficient to reduce the area of the impurity region overlapping with the gate electrode and the gate insulating film in the GOLD structure TFT. Reliability can be obtained. Specifically, sufficient reliability can be obtained even if the size of the portion that becomes the tapered portion of the gate electrode is reduced in the GOLD structure TFT.
[0137]
Further, in the GOLD structure TFT, the parasitic capacitance increases as the gate insulating film becomes thin. However, if the parasitic capacitance is reduced by reducing the size of the tapered portion of the gate electrode (first conductive layer), the f characteristic is also improved. As a result, the TFT can be operated at a higher speed and has sufficient reliability.
[0138]
Note that also in the pixel TFT of the pixel portion 207, reduction of off-state current and variation are realized by irradiation with the second laser light.
[0139]
In this embodiment, an example of manufacturing an active matrix substrate for forming a reflective display device is shown. However, when a pixel electrode is formed of a transparent conductive film, a photomask is increased by one, but a transmissive display is provided. A device can be formed.
[0140]
[Example 2]
In this embodiment, a process for manufacturing an active matrix liquid crystal display device from the active matrix substrate manufactured in Embodiment 1 will be described below. FIG. 9 is used for the description.
[0141]
First, after obtaining the active matrix substrate in the state of FIG. 8 according to Example 1, an alignment film is formed on the active matrix substrate of FIG. 8 and a rubbing process is performed. In this embodiment, before the alignment film is formed, columnar spacers for maintaining the distance between the substrates are formed at desired positions by patterning an organic resin film such as an acrylic resin film. Further, instead of the columnar spacers, spherical spacers may be scattered over the entire surface of the substrate.
[0142]
Next, a counter substrate is prepared. The counter substrate is provided with a color filter in which a colored layer and a light shielding layer are arranged corresponding to each pixel. Further, a light shielding layer was also provided in the drive circuit portion. A flattening film covering the color filter and the light shielding layer was provided. Next, a counter electrode made of a transparent conductive film was formed on the planarizing film in the pixel portion, an alignment film was formed on the entire surface of the counter substrate, and a rubbing process was performed.
[0143]
Then, the active matrix substrate on which the pixel portion and the driving circuit are formed and the counter substrate are bonded together with a sealant. A filler is mixed in the sealing material, and two substrates are bonded to each other with a uniform interval by the filler and the columnar spacer. Thereafter, a liquid crystal material is injected between both substrates and completely sealed with a sealant (not shown). A known liquid crystal material may be used as the liquid crystal material. In this way, an active matrix liquid crystal display device is completed. If necessary, the active matrix substrate or the counter substrate is divided into a desired shape. Furthermore, a polarizing plate or the like was appropriately provided using a known technique. And FPC was affixed using the well-known technique.
[0144]
The structure of the liquid crystal module thus obtained will be described with reference to the top view of FIG.
[0145]
A pixel portion 304 is disposed in the center of the active matrix substrate 301. A source signal line driver circuit 302 for driving the source signal line is disposed above the pixel portion 304. On the left and right sides of the pixel portion 304, gate signal line driving circuits 303 for driving the gate signal lines are arranged. In the example shown in this embodiment, the gate signal line driver circuit 303 is arranged symmetrically with respect to the pixel portion, but this may be arranged only on one side, and the designer may consider the size of the substrate of the liquid crystal module. May be appropriately selected. However, considering the operation reliability and driving efficiency of the circuit, the symmetrical arrangement shown in FIG. 9 is desirable.
[0146]
A signal is input to each drive circuit from a flexible printed circuit (FPC) 305. The FPC 305 opens a contact hole in the interlayer insulating film and the resin film so as to reach the wiring arranged up to a predetermined place on the substrate 301, forms a connection electrode 309, and then crimps it through an anisotropic conductive film or the like. Is done. In this example, the connection electrode was formed using ITO.
[0147]
A sealant 307 is applied to the periphery of the driving circuit and the pixel portion along the outer periphery of the substrate, and a predetermined gap (a space between the substrate 301 and the counter substrate 306) is maintained by the spacer 310 formed on the active matrix substrate in advance. In this state, the counter substrate 306 is attached. Thereafter, a liquid crystal element is injected from a portion where the sealant 307 is not applied and sealed with the sealant 308. The liquid crystal module is completed through the above steps.
[0148]
Although an example in which all the drive circuits are formed on the substrate is shown here, several ICs may be used as part of the drive circuit.
[0149]
Further, this embodiment can be freely combined with the first embodiment.
[0150]
[Example 3]
In Example 1, an example of a reflective display device in which a pixel electrode is formed of a reflective metal material is shown. However, in this embodiment, a transmissive display in which a pixel electrode is formed of a light-transmitting conductive film. An example of an apparatus is shown.
[0151]
Since the steps up to the formation of the interlayer insulating film are the same as those in the first embodiment, they are omitted here. After an interlayer insulating film is formed according to Embodiment 1, a pixel electrode 601 made of a light-transmitting conductive film is formed. As the light-transmitting conductive film, ITO (indium tin oxide alloy), indium oxide zinc oxide alloy (In₂O_Three—ZnO), zinc oxide (ZnO), or the like may be used.
[0152]
Thereafter, contact holes are formed in the interlayer insulating film 600. Next, a connection electrode 602 which overlaps with the pixel electrode is formed. The connection electrode 602 is connected to the drain region through a contact hole. In addition, the source electrode or drain electrode of another TFT is formed simultaneously with this connection electrode.
[0153]
Although an example in which all the drive circuits are formed on the substrate is shown here, several ICs may be used as part of the drive circuit.
[0154]
An active matrix substrate is formed as described above. Using this active matrix substrate, a liquid crystal module is manufactured in accordance with Embodiment 2, provided with a backlight 604 and a light guide plate 605, and covered with a cover 606, an active matrix type as shown in FIG. A liquid crystal display device is completed. Note that the cover and the liquid crystal module are bonded together using an adhesive or an organic resin. In addition, when the substrate and the counter substrate are bonded to each other, the organic resin may be filled between the frame and the substrate by being surrounded by a frame and bonded. Further, since it is a transmissive type, the polarizing plate 603 is attached to both the active matrix substrate and the counter substrate.
[0155]
Further, this embodiment can be freely combined with Embodiment 1 or Embodiment 2.
[0156]
[Example 4]
In this embodiment, an example of manufacturing a light-emitting display device including an EL (Electro Luminescence) element is shown in FIG.
[0157]
11A is a top view illustrating the EL module, and FIG. 11B is a cross-sectional view taken along line A-A ′ of FIG. 11A. A pixel portion 902, a source side driver circuit 901, and a gate side driver circuit 903 are formed over a substrate 900 (eg, a glass substrate, a crystallized glass substrate, or a plastic substrate) having an insulating surface. These pixel portions and driving circuits can be obtained according to the above embodiment.
[0158]
Reference numeral 918 denotes a sealing material, and 919 denotes a DLC film. The pixel portion and the driving circuit portion are covered with a sealing material 918, and the sealing material is covered with a protective film 919. Further, it is sealed with a cover material 920 using an adhesive. In order to withstand deformation due to heat or external force, the cover material 920 is preferably made of the same material as that of the substrate 900, for example, a glass substrate, and is processed into a concave shape (depth 3 to 10 μm) shown in FIG. . Further, it is desirable to form a recess (depth 50 to 200 μm) where the desiccant 921 can be installed by processing. In addition, when manufacturing an EL module by multi-chamfering, after bonding the substrate and the cover material, the CO₂You may cut | disconnect so that an end surface may correspond using a laser etc.
[0159]
Reference numeral 908 denotes wiring for transmitting signals input to the source side driver circuit 901 and the gate side driver circuit 903, and receives a video signal and a clock signal from an FPC (flexible printed circuit) 909 serving as an external input terminal. Although only the FPC is shown here, a printed wiring board (PWB) may be attached to the FPC. The light-emitting device in this specification includes not only a light-emitting device body but also a state in which an FPC or a PWB is attached thereto.
[0160]
Next, a cross-sectional structure is described with reference to FIG. An insulating film 910 is provided over the substrate 900, and a pixel portion 902 and a gate side driver circuit 903 are formed above the insulating film 910. The pixel portion 902 is electrically connected to the current control TFT 911 and its drain. The pixel electrode 912 is formed by a plurality of pixels. The gate side driver circuit 903 is formed using a CMOS circuit in which an n-channel TFT 913 and a p-channel TFT 714 are combined.
[0161]
These TFTs (including 911, 913, and 914) may be manufactured according to the n-channel TFT 201 of the first embodiment and the p-channel TFT 202 of the first embodiment.
[0162]
The insulating film provided between the TFT and the EL element not only blocks the diffusion of impurity ions such as alkali metal ions and alkaline earth metal ions, but also actively impurities such as alkali metal ions and alkaline earth metal ions. Materials that adsorb ions are preferred, and materials that can withstand subsequent process temperatures are suitable. An example of a material that meets these conditions is a silicon nitride film containing a large amount of fluorine. The concentration of fluorine contained in the silicon nitride film is 1 × 10¹⁹/ Cm^ThreeAs described above, the fluorine composition ratio in the silicon nitride film is preferably 1 to 5%. Fluorine in the silicon nitride film is combined with alkali metal ions, alkaline earth metal ions, etc., and is adsorbed in the film. As another example, an organic resin film containing fine particles made of an antimony (Sb) compound, a tin (Sn) compound, or an indium (In) compound that adsorbs alkali metal ions, alkaline earth metal ions, etc., for example, antimony pentoxide Fine particles (Sb₂O_Five・ NH₂An organic resin film containing O) is also included. This organic resin film contains fine particles having an average particle diameter of 10 to 20 nm and has a very high light transmittance. The antimony compound represented by the antimony pentoxide fine particles easily adsorbs impurity ions such as alkali metal ions and alkaline earth metal ions.
[0163]
The pixel electrode 912 functions as an anode of the light emitting element (EL element). A bank 915 is formed on both ends of the pixel electrode 912, and an EL layer 916 and a cathode 917 of a light emitting element are formed on the pixel electrode 912.
[0164]
As the EL layer 916, an EL layer (a layer for emitting light and moving carriers therefor) may be formed by freely combining a light-emitting layer, a charge transport layer, or a charge injection layer. For example, a low molecular organic EL material or a high molecular organic EL material may be used. In addition, a thin film made of a light emitting material (singlet compound) that emits light (fluorescence) by singlet excitation or a thin film made of a light emitting material (phosphorescence) that emits light (phosphorescence) by triplet excitation can be used as the EL layer. It is also possible to use an inorganic material such as silicon carbide for the charge transport layer or the charge injection layer. As these organic EL materials and inorganic materials, known materials can be used.
[0165]
The cathode 917 also functions as a wiring common to all pixels, and is electrically connected to the FPC 909 via the connection wiring 908. Further, all elements included in the pixel portion 902 and the gate side driver circuit 903 are covered with a cathode 917, a sealant 918, and a protective film 919.
[0166]
Note that as the sealant 918, a material that is as transparent or translucent as possible to visible light is preferably used. Further, the sealant 918 is desirably a material that does not transmit moisture and oxygen as much as possible.
[0167]
In addition, after completely covering the light emitting element with the sealant 918, it is preferable to provide a protective film 919 made of a DLC film or the like on the surface (exposed surface) of the sealant 918 at least as shown in FIG. Further, a protective film may be provided on the entire surface including the back surface of the substrate. Here, it is necessary to pay attention so that a protective film is not formed on the portion where the external input terminal (FPC) is provided. The protective film may be prevented from being formed using a mask, or the protective film may be prevented from being formed by covering the external input terminal portion with a tape such as a masking tape used in a CVD apparatus.
[0168]
By encapsulating the light emitting element with the sealing material 918 and the protective film with the structure as described above, the light emitting element can be completely shut off from the outside, and a substance that promotes deterioration due to oxidation of the EL layer such as moisture or oxygen from the outside. Can be prevented from entering. Therefore, a highly reliable light-emitting device can be obtained.
[0169]
Alternatively, the pixel electrode may be a cathode, and an EL layer and an anode may be stacked to emit light in the direction opposite to that in FIG. An example is shown in FIG. Since the top view is the same, it is omitted.
[0170]
The cross-sectional structure shown in FIG. 12 will be described below. As the substrate 1000, a semiconductor substrate or a metal substrate can be used in addition to a glass substrate or a quartz substrate. An insulating film 1010 is provided over the substrate 1000, and a pixel portion 1002 and a gate side driver circuit 1003 are formed above the insulating film 1010. The pixel portion 1002 is electrically connected to the current control TFT 1011 and its drain. The pixel electrode 1012 is formed by a plurality of pixels. The gate side driver circuit 1003 is formed using a CMOS circuit in which an n-channel TFT 1013 and a p-channel TFT 1014 are combined.
[0171]
The pixel electrode 1012 functions as a cathode of the light emitting element. A bank 1015 is formed at both ends of the pixel electrode 1012, and an EL layer 1016 and an anode 1017 of a light emitting element are formed on the pixel electrode 1012.
[0172]
The anode 1017 also functions as a wiring common to all pixels, and is electrically connected to the FPC 1009 through the connection wiring 1008. Further, all elements included in the pixel portion 1002 and the gate side driver circuit 1003 are covered with an anode 1017, a sealant 1018, and a protective film 1019 made of DLC or the like. Further, the cover material 1021 and the substrate 1000 were bonded together with an adhesive. Further, the cover material is provided with a recess, and a desiccant 1021 is provided.
[0173]
Note that as the sealant 1018, it is preferable to use a material that is as transparent or translucent as possible to visible light. The sealing material 1018 is desirably a material that does not transmit moisture and oxygen as much as possible.
[0174]
In FIG. 12, since the pixel electrode is the cathode and the EL layer and the anode are stacked, the light emission direction is the direction of the arrow shown in FIG.
[0175]
In this embodiment, a TFT with high electrical characteristics and high reliability obtained in Embodiment 1 is used, so that a light-emitting element with higher reliability than a conventional element can be formed. In addition, a high-performance electric appliance can be obtained by using a light-emitting device having such a light-emitting element as a display portion.
[0176]
Note that this embodiment can be freely combined with Embodiment 1.
[0177]
[Example 5]
The driver circuit and the pixel portion formed by implementing the present invention can be used for various modules (active matrix liquid crystal module, active matrix EL module, active matrix EC module). That is, by implementing the present invention, all electronic devices incorporating them are completed.
[0178]
Such electronic devices include video cameras, digital cameras, head mounted displays (goggles type displays), car navigation systems, projectors, car stereos, personal computers, personal digital assistants (mobile computers, mobile phones, electronic books, etc.), etc. Can be mentioned. Examples of these are shown in FIGS.
[0179]
FIG. 13A illustrates a personal computer, which includes a main body 2001, an image input portion 2002, a display portion 2003, a keyboard 2004, and the like.
[0180]
FIG. 13B illustrates a video camera, which includes a main body 2101, a display portion 2102, an audio input portion 2103, operation switches 2104, a battery 2105, an image receiving portion 2106, and the like.
[0181]
FIG. 13C illustrates a mobile computer, which includes a main body 2201, a camera unit 2202, an image receiving unit 2203, operation switches 2204, a display unit 2205, and the like.
[0182]
FIG. 13D shows a goggle type display, which includes a main body 2301, a display portion 2302, an arm portion 2303, and the like.
[0183]
FIG. 13E shows a player using a recording medium (hereinafter referred to as a recording medium) on which a program is recorded, and includes a main body 2401, a display portion 2402, a speaker portion 2403, a recording medium 2404, operation switches 2405, and the like. This player uses a DVD (Digital Versatile Disc), CD, or the like as a recording medium, and can perform music appreciation, movie appreciation, games, and the Internet.
[0184]
FIG. 13F illustrates a digital camera, which includes a main body 2501, a display portion 2502, an eyepiece portion 2503, an operation switch 2504, an image receiving portion (not shown), and the like.
[0185]
FIG. 14A illustrates a front type projector, which includes a projection device 2601, a screen 2602, and the like. The third embodiment can be applied to the liquid crystal module 2808 that constitutes a part of the projection apparatus 2601 to complete the entire apparatus.
[0186]
FIG. 14B shows a rear projector, which includes a main body 2701, a projection device 2702, a mirror 2703, a screen 2704, and the like. The third embodiment can be applied to the liquid crystal module 2808 that constitutes a part of the projection apparatus 2702 to complete the entire apparatus.
[0187]
FIG. 14C is a diagram showing an example of the structure of the projection devices 2601 and 2702 in FIGS. 14A and 14B. The projection devices 2601 and 2702 include a light source optical system 2801, mirrors 2802 and 2804 to 2806, a dichroic mirror 2803, a prism 2807, a liquid crystal module 2808, a phase difference plate 2809, and a projection optical system 2810. Projection optical system 2810 includes an optical system including a projection lens. Although the present embodiment shows a three-plate type example, it is not particularly limited, and for example, a single-plate type may be used. Further, the practitioner may appropriately provide an optical system such as an optical lens, a film having a polarization function, a film for adjusting a phase difference, or an IR film in the optical path indicated by an arrow in FIG. Good.
[0188]
FIG. 14D shows an example of the structure of the light source optical system 2801 in FIG. In this embodiment, the light source optical system 2801 includes a reflector 2811, a light source 2812, lens arrays 2813 and 2814, a polarization conversion element 2815, and a condenser lens 2816. Note that the light source optical system illustrated in FIG. 14D is an example and is not particularly limited. For example, the practitioner may appropriately provide an optical system such as an optical lens, a film having a polarization function, a film for adjusting a phase difference, or an IR film in the light source optical system.
[0189]
However, the projector shown in FIG. 14 shows a case where a transmissive electro-optical device is used, and an application example in a reflective electro-optical device and an EL module is not shown.
[0190]
FIG. 15A shows a cellular phone, which includes a main body 2901, an audio output portion 2902, an audio input portion 2903, a display portion 2904, operation switches 2905, an antenna 2906, an image input portion (CCD, image sensor, etc.) 2907, and the like.
[0191]
FIG. 15B illustrates a portable book (electronic book), which includes a main body 3001, display portions 3002 and 3003, a storage medium 3004, operation switches 3005, an antenna 3006, and the like.
[0192]
FIG. 15C illustrates a display, which includes a main body 3101, a support base 3102, a display portion 3103, and the like.
[0193]
Incidentally, the display shown in FIG. 15C is a medium or small size display, for example, a screen size of 5 to 20 inches. Further, in order to form a display portion having such a size, it is preferable to use a substrate having a side of 1 m and perform mass production by performing multiple chamfering.
[0194]
As described above, the applicable range of the present invention is so wide that the present invention can be applied to methods for manufacturing electronic devices in various fields. Moreover, the electronic device of a present Example is realizable even if it uses the structure which consists of what combination of Examples 1-4.
[0195]
【The invention's effect】
According to the present invention, a high concentration in the film, specifically 1 × 10²⁰/ Cm^Three~ 1x10^{twenty one}/ Cm^ThreeThe concentration of fluorine in the film is 1 × 10¹⁷/ Cm^ThreeThe following amorphous silicon film can be formed by plasma CVD.
[0196]
In addition, according to the present invention, it is possible to obtain a semiconductor film having a crystal structure in which a metal element that sufficiently promotes crystallization is reduced or removed. In the TFT using the semiconductor film as an active layer, improvement in electrical characteristics and The variation between the elements can be reduced. In particular, in a liquid crystal display device, display unevenness due to variations in TFT characteristics can be reduced.
[0197]
In addition, in a semiconductor device having an OLED, an on-current (I) of a TFT (TFT that supplies current to an OLED arranged in a driving circuit or a pixel) arranged so that a constant current flows through the pixel electrode._on) Variation and luminance variation can be reduced.
[0198]
In addition to the metal element that promotes crystallization according to the present invention, other metal elements (such as Fe and Cu) that become impurities can be removed or reduced.
[Brief description of the drawings]
FIGS. 1A and 1B illustrate a manufacturing process of a TFT. FIGS.
FIGS. 2A and 2B are SIMS data (RF power dependence) indicating an argon concentration, and FIG. 2B is SIMS data indicating a fluorine concentration. (Experiment 1)
3A is SIMS data indicating oxygen concentration, and FIG. 3B is SIMS data indicating nitrogen concentration. (Experiment 1)
4A is SIMS data (pressure dependency) showing an argon concentration, and FIG. 4B is SIMS data showing a fluorine concentration. (Experiment 2)
5A is SIMS data indicating oxygen concentration, and FIG. 5B is SIMS data indicating nitrogen concentration. (Experiment 2)
FIGS. 6A and 6B are diagrams illustrating a manufacturing process of an active matrix substrate. FIGS.
FIG. 7 shows an active matrix substrate.
FIG. 8 shows an active matrix substrate.
FIG. 9 is a diagram illustrating an appearance of an AM-LCD.
FIG. 10 illustrates a transmissive liquid crystal display device.
FIG. 11 is a diagram showing a top surface and a cross section of an EL module.
FIG. 12 is a view showing a cross section of an EL module.
FIG 13 illustrates an example of an electronic device.
FIG 14 illustrates an example of an electronic device.
FIG 15 illustrates an example of an electronic device.
FIG. 16 is a diagram showing spectroscopic spectrum data by an FT-IR method.
FIG. 17 is a graph showing the argon concentration on the surface of the amorphous silicon film of the present invention.

Claims (6)

A first step of forming a first semiconductor film having an amorphous structure on an insulating surface;
A second step of adding a metal element to the first semiconductor film having the amorphous structure;
A third step of crystallizing the first semiconductor film to form a first semiconductor film having a crystal structure;
A fourth step of forming a barrier layer on the surface of the first semiconductor film having the crystal structure;
A second semiconductor film containing a rare gas element at a concentration of 1 × 10 ²⁰ / cm ³ to 1 × 10 ²¹ / cm ³ on the barrier layer by plasma CVD is used as a source gas of monosilane, a rare gas, and hydrogen. And a fifth step of forming by generating plasma,
A sixth step of removing or reducing the metal element in the first semiconductor film having a crystal structure by gettering the metal element to the second semiconductor film;
A method for manufacturing a semiconductor device, comprising: a seventh step of removing the second semiconductor film. A first step of forming a first semiconductor film having an amorphous structure on an insulating surface;
A second step of adding a metal element to the first semiconductor film having the amorphous structure;
A third step of crystallizing the first semiconductor film to form a first semiconductor film having a crystal structure;
A fourth step of forming a barrier layer on the surface of the first semiconductor film having the crystal structure;
A second semiconductor film containing a rare gas element at a concentration of 1 × 10 ²⁰ / cm ³ to 1 × 10 ²¹ / cm ³ on the barrier layer by plasma CVD is used as a source gas of monosilane, a rare gas, and hydrogen. And a fifth step of forming by generating plasma,
A sixth step of removing or reducing the metal element in the first semiconductor film having a crystal structure by gettering the metal element to the second semiconductor film;
A seventh step of removing the second semiconductor film;
And an eighth step of removing the barrier layer. In any one of Claim 1 or Claim 2,
The method for manufacturing a semiconductor device, wherein the rare gas element is one or more selected from He, Ne, Ar, Kr, and Xe. In any one of Claims 1 thru | or 3,
The method of manufacturing a semiconductor device, wherein the metal element is one or more selected from Fe, Ni, Co, Ru, Rh, Pd, Os, Ir, Pt, Cu, and Au. In any one of Claims 1 thru | or 4,
The plasma generating conditions for forming the second semiconductor film are as follows: the input RF power density is 0.333 W / cm. ² A manufacturing method of a semiconductor device, which is described above. In any one of Claims 1 thru | or 5,
The fluorine concentration of the second semiconductor film is 2 × 10 ¹⁶ / Cm ³ ~ 8x10 ¹⁶ / Cm ³ And the nitrogen concentration is 1 × 10 ¹⁶ / Cm ³ ~ 1x10 ¹⁷ / Cm ³ And the oxygen concentration is 1 × 10 ¹⁸ / Cm ³ ~ 3x10 ¹⁸ / Cm ³ And the carbon concentration is 1 × 10 ¹⁶ / Cm ³ ~ 5x10 ¹⁷ cm ³ A method for manufacturing a semiconductor device.

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