Embodiments of the present invention use a filled tetrahedral (FT) semiconductor as a band engineering method of modulating the band structure of a semiconductor. The term “FT semiconductor” conventionally refers to a crystalline solid in which a rare gas atom or a diatomic molecule with an electron configuration of a closed shell is introduced into an “interstitial site” of a matrix semiconductor having a tetrahedral structure such as a diamond structure or a zinc blende structure. The effects of the FT semiconductor, the core of the present invention, will be described in detail.
Described in the first step are (1) the reason why an indirect semiconductor such as silicon has an indirect band structure, and (2) the reason why the indirect semiconductor has a low absorption coefficient. Then described are (3) the feature of the FT semiconductor (rare gas-containing FT semiconductor and molecule-containing FT semiconductor), and (4) the principle of enhanced absorption. Further described is (5) a novel FT semiconductor, i.e., a pendant type FT semiconductor, which constitutes the important part of the present invention.
(1) Band Structure of the Indirect Semiconductor:
As shown in
(2) Optical Characteristics of an Indirect Semiconductor:
In the indirect semiconductor, the electric dipole transition is optically forbidden. Thus, the indirect semiconductor exhibits only weak absorption attributed to a phonon-assisted indirect transition in a low energy region near the band edge (i.e., it has a low absorption coefficient). In contrast to the above, a direct transition attributed to an electric dipole transition occurs in a direct semiconductor such as GaAs, leading to significant absorption (i.e., it has a high absorption coefficient). The difference between the two semiconductors is mainly caused by whether the two selection rules given below are satisfied.
One of the selection rules relates to the wave number, i.e., the requirement that the energy gap should be made smallest at the specified wave number. The other selection rule relates to symmetry of the wave function, i.e., the requirement that, in the wave number that makes the gap minimum, one of the conduction band and the valence band should be an even function and the other should be an odd function.
It should be noted in respect of the selection rule of the symmetry that the intensity of the emission and the absorption between two levels is given by <upper level|transition dipole moment μ|lower level>. For a semiconductor in which the two levels are represented by an s-orbital (even function) and a p-orbital (odd function) in the vicinity of an atomic orbital, μ corresponds to an odd function, so that the following relation is met, which means that this semiconductor is optically allowed.
<s|μ|p>=∫even·odd·odd dr≠0.
On the other hand, for a semiconductor in which the two levels are represented by the p-orbital, the following relation is met, which means that this semiconductor is optically forbidden:
<p|μ|p>=∫odd·odd·odd dr=0.
In the direct semiconductor, the gap is made minimum at the Γ point so as to satisfy the selection rule of the wave number. In the direct semiconductor, the wave functions of the conduction band and the valence band are expressed by the s-orbital and the p-orbital, respectively, with the result that the selection rule of the symmetry is also satisfied.
On the other hand, in the indirect semiconductor, the conduction band and the valence band differ from each other in the wave number making the gap minimum, resulting in failure to satisfy the selection rule of the wave number. In addition, since the wave functions for both conduction band and valence band are represented by the p-orbital, the selection rule of the symmetry is not satisfied either. It follows that the indirect semiconductor is optically forbidden.
(3) FT Semiconductor:
The FT semiconductor is a theoretic material that was discovered in 1984 in the process of calculating the conduction band structure of GaAs (see H. W. A. M. Rompa et al., Phys. Rev. Lett., 52, 675 [1984] and D. M. Wood et al., Phys. Review B31, 2570 [1985]). Rompa et al., who discovered the theoretic substance, found through the band calculation that FT-GaAs having He introduced into the interstitial sites of GaAs exhibits an increase in X point energy.
The present invention uses the FT semiconductor as a new band engineering method and applies the FT semiconductor structure, which allows the X point energy to be controlled, to an indirect semiconductor such as silicon. This imparts a significant light absorption to the indirect semiconductor, which originally exhibits only an insignificant light absorption.
As described above, the term “FT semiconductor” conventionally refers to a crystalline solid in which a rare gas atom or a diatomic molecule with an electron configuration of a closed shell is introduced into an “interstitial site” of a matrix semiconductor having a tetrahedral structure such as a diamond structure or a zinc blende structure.
Description will be given of the difference between the band structures of the ordinary crystalline silicon and the FT semiconductor.
(4) Principle of Enhancement of Absorption in the FT Semiconductor:
As shown in
In the well-known FT semiconductor, the FT structure is formed by introducing a rare gas atom (or molecule) with an electron configuration of a closed shell into the space in the interstitial site. The FT structure formed excludes an electron from the interstitial site to increase the energy of Xc and Γv attributed to the p-orbital. However, the Γc energy attributed to the anti-bonding s-orbital is almost unaffected. This reduces, therefore, the difference between the Γc energy and the Γv energy to lower the level of Γc relative to Γv, resulting in a direct transition. This increases the light absorption.
The above discussions will be summarized with reference to an energy band diagram shown in
The presence of an atom in the interstitial site may form a deep or defect level within the band gap, which may reduce a light current. However, in the FT structure, the atom (or molecule) of the closed shell structure having a wide gap is inserted into the interstitial site, which prevents in principle the formation of such a level.
(5) Problems with the Rare Gas-Containing or Molecule-Containing FT Semiconductor:
However, the rare gas-containing or molecule-containing FT semiconductor proposed by Rompa et al. is believed to be thermally unstable because the inserted substance can move within the crystal and, thus, not to be suitable for practical use.
Concerning the FT semiconductor, the result of an experiment is reported that, if rare gas atoms are ion-implanted in a silicon wafer, photoluminescence (PL emission) is generated in the energy region in the vicinity of 1 eV, though the mechanism of the PL emission is not clarified (see N. Burger et al., Phys. Rev. Lett., 52, 1645 [1984]). However, if the wafer in which the rare gas atoms have been ion-implanted is annealed, the PL emission is caused to disappear, though the reason therefore is again not clear. It is believed that the disappearance of PL emission is derived from the fact that, since the rare gas atom is not chemically bonded with the silicon atom, the rare gas atom is diffused within the silicon crystal and may be finally released from the wafer.
Accordingly, even if the rare gas-containing or molecule-containing FT semiconductor can be formed into the FT structure, the resultant structure is easily expected to be poor in thermal stability. In short, there is a problem that the conventional FT semiconductor will not be a practical material system.
(6) Novel Pendant Type FT Semiconductor:
Where a pendant type FT semiconductor is to be realized by using silicon, it is possible to use an n- or p-type dopant, which has already been used in the actual LSI process, can be used as it is for the dopant D (or A). This facilitates the manufacture of the pendant type FT semiconductor so as to reduce the manufacturing cost thereof.
For the pendant type FT semiconductor according to the embodiment, whether a light receiving function can be imparted to the indirect semiconductor is important as in the case of the rare gas-containing or molecule-containing FT semiconductor.
According to the results of calculations, in the case where the PF pair concentration is zero shown in
In conclusion, the pendant type FT semiconductor, like the rare gas-containing or molecule-containing FT semiconductor, is considered to produce the effect of band-modulating an indirect semiconductor into a direct semiconductor to sharply increase the absorption coefficient of the inter-band transition. The absorption coefficient is expected to increase consistently with the pair concentration.
In the embodiments, combinations of the matrix semiconductor, dopant D or A, and heteroatom Z contained in the pendant type FT semiconductor are exemplified as follows.
(1) The matrix semiconductor is selected from the group consisting of IVb elemental semiconductors and IVb-IVb compound semiconductors, the dopant D is selected from the group consisting of Va elements and Vb elements, and the heteroatom Z is selected from the group consisting of VIIb elements.
(2) The matrix semiconductor is selected from the group consisting of IVb elemental semiconductors and IVb-IVb compound semiconductors, the dopant A is selected from the group consisting of IIIa elements and IIIb elements, and the heteroatom Z is selected from the group consisting of Ia elements and Ib elements.
Combinations of the matrix semiconductor other than the IVb elemental semiconductor, the dopant D or A, and the heteroatom Z are exemplified as follows.
(3) The matrix semiconductor is selected from the group consisting of IIIb-Vb compound semiconductors, the dopant D is selected from the group consisting of IVa elements and IVb elements and substituted for the IIIb atom at a lattice site, and the heteroatom Z is selected from the group consisting of VIIb elements.
(4) The matrix semiconductor is selected from the group consisting of IIIb-Vb compound semiconductors, the dopant A is selected from the group consisting of IIa elements and IIb elements and substituted for the IIIb atom at a lattice site, and the heteroatom Z is selected from the group consisting of Ia elements and Ib elements.
(5) The matrix semiconductor is selected from the group consisting of IIIb-Vb compound semiconductors, the dopant D is selected from the group consisting of VIa elements and VIb elements and substituted for the Vb atom at a lattice site, and the heteroatom Z is selected from the group consisting of VIIb elements.
(6) The matrix semiconductor is selected from the group consisting of IIIb-Vb compound semiconductors, the dopant A is selected from the group consisting of IVa elements and IVb elements and substituted for the Vb atom at a lattice site, and the heteroatom Z is selected from the group consisting of Ia elements and Ib elements.
The matrix semiconductor can be exemplified as follows. An example of the IVb elemental semiconductor includes silicon. The IVb-IVb compound semiconductor is selected from the group consisting of SiC, GeC, SixGe1-x (0<x<1) and SixGeyC1-x-y (0<x<1, 0<y<1, 0<x+y<1). The IIIb-Vb compound semiconductor is selected from the group consisting of BN, BP, AlP, AlAs, AlSb and GaP.
The dopant D or A, and the heteroatom Z can be exemplified as follows. The Ia element is selected from the group consisting of Li, Na, K, Rb and Cs. The IIa element is selected from the group consisting of Be, Mg, Ca, Sr, and Ba. The IIIa element is selected from the group consisting of Sc, Y, La and Lu. The IVa element is selected from the group consisting of Ti, Zr and Hf. The Va element is selected from the group consisting of V, Nb and Ta. The VIa element is selected from the group consisting of Cr, Mo and W. The Ib element is selected from the group consisting of Cu, Ag, and Au. The IIb element is selected from the group consisting of Zn, Cd, and Hg. The IIIb element is selected from the group consisting of B, Al, Ga, In and Tl. The IVb element is selected from the group consisting of C, Si, Ge, Sn and Pb. The Vb element is selected from the group consisting of N, P, As, Sb, and Bi. The VIb element is selected from the group consisting of O, S, Se and Te. The VIIb element is selected from the group consisting of F, Cl, Br and I.
The optical receiving device according to an embodiment has a photocarrier generation layer (photoelectric conversion layer) comprising an FT semiconductor. The positions of electrodes relative to the photoelectric layer are not particularly limited.
In the optical receiving device of the vertical type shown in
In this optical receiving device, light carriers (electrons and holes) generated in the photocarrier generation layer are drifted in the vertical direction to obtain electrons from the n electrode 4 via the n+ region 1 and to obtain holes from the p electrode 6 via the p+ region 3, and thus a light current is produced.
In the optical receiving device of the lateral type shown in
In this optical receiving device, light carriers (electrons and holes) generated in the photocarrier generation layer 13 are drifted in the lateral direction to obtain electrons from the n electrode 17 via the n+ region 15 and to obtain holes from the p electrode 18 via the p+ region 16, and thus a light current is produced.
In both vertical and lateral type optical receiving devices, the buried oxide film is formed for preventing current leakage. However, the buried oxide film need not necessarily be formed if the current leakage can be prevented by any means such as the element structure, substrate resistivity, and circuit.
Each of
A method of forming a photocarrier generation layer having an FT structure will now be described with reference to
A Si wafer 21 is prepared as shown in
As shown in
In the step shown in
Further, the other steps are carried out to enable the production of such an optical receiving device as shown in
As described above, a photocarrier generation layer having an FT structure can be formed in a matrix semiconductor by the method employing the combination of ion implantation and annealing. Alternatively, a photocarrier generation layer having an FT structure can be formed by a combination of thermal diffusion and annealing. A photocarrier generation layer having an FT structure can also be formed by any other method.
If the dopant D at the lattice point is bonded to the heteroatom Z in the interstitial site as in the case of the PF pair, an inherent vibration mode differing from the lattice vibration of the matrix semiconductor is generated. As a result, it is possible to analyze directly the FT structure by infrared spectroscopy or Raman spectroscopy. When it comes to an example of the PF pair, the calculation of the standard vibration indicates that a vibration mode appears in the vicinity of the wave number of 150 to 200 cm−1. In this fashion, evaluation of the vibration mode provides one of effective means of examining the presence of the FT structure.
As an indirect and simple method of detecting the presence of a DZ (or AZ) pair, it is possible to employ an electrical measurement such as resistance measurement or Hall measurement. In the case of using an n-type (or p-type) dopant, the substrate before doping the heteroatom Z in the interstitial site exhibits n-type or p-type conductivity and, thus, has a low resistivity. If the dopant D (or A) is paired with the heteroatom Z, charge compensation reduces free carriers to increase the resistivity of the substrate. Thus, it is possible to detect whether the DZ (or AZ) pair has been formed by comparing the resistances or the carrier concentrations before and after the doping of the heteroatom Z.
The present invention will be described in more detail with reference to specific embodiments.
A silicon optical receiving device of the lateral type, which is constructed as shown in
To determine whether a PF pair of a pendant type FT structure is formed in the photocarrier generation layer 13, it is effective to examine the vibration mode inherent in the PF pair, which can be detected by microspectroscopy of the photocarrier generation layer. A method for easily checking the PF pair formation is to form a PF-doped region having the same composition as that of the photocarrier generation layer and a region doped only with P on the surface of a high-resistivity substrate and then to compare these two doped regions for sheet resistance or carrier concentration. The formation of a PF pair leads to charge compensation to increase the resistivity of the PF-doped region above that of the region doped only with P, while reducing the carrier concentration of the PF-doped region below that of the region doped only with P.
As seen from the result of the band calculation in
To effectively derive the light current which has been generated in the photocarrier generation layer via the electrodes, a driving voltage V is applied to between the n electrode 17 and the p electrode 18 (not shown in
As described above, the pendant type FT semiconductor modulating the energy band is very effective for imparting a high light absorbing function to the photocarrier generation layer of the silicon-based optical receiving device to increase the operating speed and sensitivity of the optical receiving device.
A device is produced which has exactly the same configuration as that of the device according to the first embodiment except that the B atom is used as the heteroatom Z in place of the F atom. The B concentration is set to 5×1021/cm3, which is equal to the F concentration in the first embodiment.
Optical signals with a wavelength of 850 nm modulated at 10 MHz are input to this optical receiving device to examine the output currents. The optical receiving device in the comparative example provides only low output currents and fails to sense the optical signals.
The insufficient output currents are due to the position of the B atom in the crystal. As widely known in the art, the B atom is a typical p-type dopant and is substituted for the lattice site, not the interstitial site. Thus, the charge compensation between the B atom and the P atom increases the resistivity of the photocarrier generation layer. However, the pendant type FT structure is not formed.
Therefore, in order to induce a high light absorbing function by forming a pendant type FT structure to modulate the band structure, sufficient consideration must be given in selecting the combination of the dopant substituted for the lattice site and the heteroatom inserted into the interstitial site.
An optical receiving device having exactly the same configuration as that in the first embodiment is produced except that the B atom, a p-type dopant, is used as the dopant D and the K atom is used as the heteroatom Z. The B concentration and K concentration as determined by SIMS are both 4×1021/cm3, and the BK pair concentration is estimated at 4×1021/cm3.
To determine whether a BK pair of the pendant type FT structure is formed in the photocarrier generation layer, it is effective to determine the vibration mode inherent in the BK pair. It can also be determined by using a simpler method based of the resistivity value or carrier concentration.
As seen from the embodiment, even with the combination of the p-type dopant and the heteroatom Z, the operating speed and sensitivity of the optical receiving device can be increased by forming a pendant type FT structure in the photocarrier generation layer to enhance light absorption.
When optical signals containing red light and near infrared light with a wavelength greater than 600 nm are selectively input to the CMOS image sensor via a filter, well contrasted output images (electrical signals) are provided.
Thus, the CMOS image sensor according to the embodiment enables sensitive image pickup even with light having a wavelength greater than 600 nm, for which the crystalline silicon exhibits only low spectral sensitivity.
When optical signals with a wavelength greater than 600 nm are selectively input to the CMOS image sensor through a filter, well contrasted output images (electrical signals) are provided.
Thus, the CCD image sensor according to the embodiment enables sensitive image pickup even with light having a wavelength greater than 600 nm, for which the crystalline silicon exhibits only low spectral sensitivity.
In the solar cell, an n+ layer 51, a photocarrier generation layer 52 comprising FT-Si, and a p+ layer 53 are stacked. A back electrode 54 is formed on a back surface of the n+ layer 51. Lattice-shaped surface electrodes 55 are formed on the surface of the p+ layer 53. Antireflection coatings 56 are formed in the areas surrounded by the surface electrodes 55.
When the solar cell is irradiated with false sunlight to determine conversion efficiency, it is found to be 50%. This value is higher than the efficiency of a solar cell comprising crystalline silicon (20 to 30%) or an amorphous silicon (10 to 15%).
Thus, the solar cell according to the embodiment can effectively absorb sunlight using the photocarrier generation layer with a high absorption coefficient, achieving a high conversion efficiency.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
Number | Date | Country | Kind |
---|---|---|---|
2006-138023 | May 2006 | JP | national |