Semiconductor wafer made of monocrystalline silicon, and method for producing same
10844515 ยท 2020-11-24
Assignee
Inventors
- Timo Mueller (Burghausen, DE)
- Walter Heuwieser (Stammham, DE)
- Michael SKROBANEK (Freiberg, DE)
- Gudrun KISSINGER (Lebus, DE)
Cpc classification
C30B15/04
CHEMISTRY; METALLURGY
H01L29/16
ELECTRICITY
C30B15/203
CHEMISTRY; METALLURGY
International classification
H01L21/02
ELECTRICITY
H01L29/16
ELECTRICITY
H01L21/78
ELECTRICITY
C30B15/04
CHEMISTRY; METALLURGY
Abstract
A semiconductor wafer comprising single-crystal silicon has defined concentrations of oxygen, nitrogen and hydrogen; the semiconductor wafer further contains BMD seeds having a density averaged over the radius of not less than 110.sup.5 cm.sup.3 and not more than 110.sup.7 cm.sup.3; surface defects having a density averaged over the radius of not less than 1100 cm.sup.2; and BMDs, whose density is not lower than a lower limit of 510.sup.8/cm.sup.3. The semiconductor wafers are produced by a process which enables obtention of the required ranges of concentrations of oxygen, nitrogen, hydrogen, BMD seeds, and BMD's.
Claims
1. A semiconductor wafer comprising single-crystal silicon with a center, an edge and a radius R between the center and the edge, an oxygen concentration of not less than 4.910.sup.17 atoms/cm.sup.3 and not more than 5.8510.sup.17 atoms/cm.sup.3; a nitrogen concentration of not less than 510.sup.12 atoms/cm.sup.3 and not more than 1.010.sup.14 atoms/cm.sup.3; a hydrogen concentration of not less than 310.sup.13 atoms/cm.sup.3 and not more than 810.sup.13 atoms/cm.sup.3; bulk micro defect (BMD) seeds whose density averaged over the radius of the semiconductor wafer, as determined by infrared (IR) tomography, is not less than 110.sup.5 cm.sup.3 and not more than 110.sup.7 cm.sup.3; surface defects whose density averaged over the radius is not less than 1100 cm as determined by optical microscopy after heat treatments of the semiconductor wafer at a temperature of 900 C. over a period of 8 h in an atmosphere of nitrogen and at a temperature of 1100 C. over a period of 2 h in an atmosphere of oxygen and hydrogen; and bulk micro defects (BMDs), whose density is not lower than a lower limit of 510.sup.8/cm.sup.3 determined by IR tomography along the radius from a radial position r=R/3 to a radial position r=R/1.15 after heat treatments of the semiconductor wafer at a temperature of 780 C. over a period of 3 h and at a temperature of 1000 C. over a period of 16 h.
2. The semiconductor wafer of claim 1, wherein a frontside of the semiconductor wafer is covered with an epitaxial layer comprising silicon.
3. The semiconductor wafer of claim 2, wherein the density of BMDs is not less than 310.sup.8/cm.sup.3 and not more than 510.sup.9/cm.sup.3, determined from the center to the edge of the semiconductor wafer for an edge exclusion of 1 mm and evaluated by IR tomography after heat treatments of the semiconductor wafer at a temperature of 780 C. over a period of 3 h and at a temperature of 1000 C. over a period of 16 h.
4. The semiconductor wafer of claim 2, wherein the density of BMDs varies by not more than 80% based on a mean density, determined along the radius from a radial position r=R/1.0791 to a radial position r=R/1.0135 and evaluated by IR tomography after heat treatments of the semiconductor wafer at a temperature of 780 C. over a period of 3 h and at a temperature of 1000 C. over a period of 16 h.
5. The semiconductor wafer of claim 3, wherein the density of BMDs varies by not more than 80% based on a mean density, determined along the radius from a radial position r=R/1.0791 to a radial position r=R/1.0135 and evaluated by IR tomography after heat treatments of the semiconductor wafer at a temperature of 780 C. over a period of 3 h and at a temperature of 1000 C. over a period of 16 h.
6. A process for producing a semiconductor wafer of claim 1 from single-crystal silicon, comprising: pulling a single crystal from a melt by the CZ method at a pulling velocity V, wherein the melt is doped with oxygen, nitrogen and hydrogen and the single crystal grows at a crystallization interface; controlling the incorporation of oxygen, nitrogen and hydrogen in a section of the single crystal having a uniform diameter in such a way that the oxygen concentration is not less than 4.910.sup.17 atoms/cm.sup.3 and not more than 5.8510.sup.17 atoms/cm.sup.3, the nitrogen concentration is not less than 510.sup.12 atoms/cm.sup.3 and not more than 1.010.sup.14 atoms/cm.sup.3 and the hydrogen concentration is not less than 310.sup.13 atoms/cm.sup.3 and not more than 810.sup.13 atoms/cm.sup.3; controlling the pulling velocity V such that it is within a span V within which the single crystal in the section having a uniform diameter grows in a P.sub.v region, wherein the pulling velocity V is in a subrange of the span which comprises 39% of the span and a lowest pulling of velocity of the subrange is 26% greater than a pulling velocity V.sub.Pv/Pi at the transition from the P.sub.v region to a P.sub.i region; and separating the semiconductor wafer from the section of the single crystal having a uniform diameter.
7. The process of claim 6, further comprising pulling the single crystal in an atmosphere comprising hydrogen, wherein the partial pressure of the hydrogen is not less than 5 Pa and not more than 18 Pa.
8. The process of claim 6, further comprising increasing the partial pressure of the hydrogen once the section of the single crystal having a uniform diameter has reached an axial length greater than 50% of an intended axial length of this section.
9. The process of claim 6, further comprising increasing the partial pressure of the hydrogen once the section of the single crystal having a uniform diameter has reached an axial length greater than 50% of an intended axial length of this section.
10. The process of claim 6, wherein an epitaxial layer of silicon is deposited on a frontside of the semiconductor wafer.
11. The process of claim 6, wherein an epitaxial layer of silicon is deposited on a frontside of the semiconductor wafer.
12. The process of claim 6, wherein an epitaxial layer of silicon is deposited on a frontside of the semiconductor wafer.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
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(3)
(4)
(5)
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(12)
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(13) A heat treatment of the semiconductor wafer or of the single crystal which is performed before the deposition of an epitaxial layer on the semiconductor wafer in order to generate and/or stabilize BMD seeds not dissolved during the deposition of the epitaxial layer is not a constituent of the process.
(14) The inventors suspect the formation of overlay defects to be caused by stresses in the crystal lattice due to excessive densities of BMDs. Such stresses can also occur if the radial progression of the density of BMDs is excessively inhomogeneous. Furthermore, an excessively low density of BMDs can also bring about overlay defects because in such a case the activity of BMDs for blocking slip in the crystal lattice, so-called pinning, is too weakly pronounced. The formation of twin dislocations is suspected to be caused by BMD seeds which are relatively large but still too small to be able to form OSF defects.
(15) The provided semiconductor wafer must therefore fulfill certain requirements. In terms of the concentration of oxygen, nitrogen and hydrogen the provided semiconductor wafer has the following properties:
(16) The oxygen concentration of the semiconductor wafer as per new ASTM is not less than 4.910.sup.17 atoms/cm.sup.3 and not more than 5.8510.sup.17 atoms/cm.sup.3, the nitrogen concentration is not less than 510.sup.12 atoms/cm.sup.3 and not more than 1.010.sup.14 atoms/cm.sup.3 and the hydrogen concentration is not less than 310.sup.13 atoms/cm.sup.3 and not more than 810.sup.13 atoms/cm.sup.3.
(17) When the oxygen concentration is lower than the lower limit then, after the deposition of an epitaxial layer on the semiconductor wafer and after a heat treatment which allows BMD seeds to grow into BMDs, BMDs whose density along the radius of the semiconductor wafer is too inhomogeneous and remains below 310.sup.8/cm.sup.3 in places or completely are formed. To be able to achieve adequate activity as internal getters the density of BMDs should be not less than 310.sup.8/cm.sup.3. The oxygen concentration must not exceed the upper limit of 5.8510.sup.17 atoms/cm.sup.3 either, because otherwise BMD seeds become too large and the semiconductor wafer after deposition of an epitaxial layer on the semiconductor wafer tends to form twin dislocations on the surface of the epitaxial layer. The oxygen concentration is preferably not more than 5.710.sup.17 atoms/cm.sup.3.
(18) When the nitrogen concentration is lower than the lower limit of 510.sup.12 atoms/cm.sup.3 this results in the same disadvantages as the oxygen concentration lower than the lower limit. The nitrogen concentration upper limit of 1.010.sup.14 atoms/cm.sup.3 must not be exceeded because otherwise after deposition of an epitaxial layer on the semiconductor wafer and after a heat treatment which allows BMD seeds to grow into BMDs the semiconductor wafer comprises BMDs whose density is excessive. The density of BMDs is excessive when the density along the radius of the semiconductor wafer exceeds an upper limit of 2.510.sup.9/cm.sup.3 in places or completely. The nitrogen concentration is preferably not more than 3.510.sup.13 atoms/cm.sup.3.
(19) The presence of hydrogen suppresses the formation of seeds of OSF defects and contributes to a uniformization of the radial progression of the density of BMDs, in particular in the edge region of the semiconductor wafer. The hydrogen concentration in the semiconductor wafer should therefore be not less than 310.sup.13 atoms/cm.sup.3. When the hydrogen concentration is smaller than the lower limit the radial progression of the density of BMDs in the edge region of the semiconductor wafer becomes too inhomogeneous. When the hydrogen concentration is greater than the upper limit of 810.sup.13 atoms/cm.sup.3 the semiconductor wafer tends after deposition of an epitaxial layer to form twin dislocations on the epitaxial layer. For this reason the single crystal of silicon from which the semiconductor wafer is separated is pulled in an atmosphere which comprises hydrogen, wherein the partial pressure of the hydrogen is preferably not less than 5 Pa and not more than 15 Pa.
(20) Observing the recited concentration ranges with respect to oxygen, nitrogen and hydrogen is not in itself sufficient to solve the problem. In addition three further properties must be fulfilled:
(21) The density of BMD seeds meaned over the radius of the semiconductor wafer, determined by IR tomography, is not less than 110.sup.5 cm.sup.3 and not more than 110.sup.7 cm.sup.3.
(22) The mean density of surface defects determined along the radius of the semiconductor wafer is not less than 1100 cm.sup.2, preferably up to 10,000 cm.sup.2, determined by optical microscopy after a first heat treatment of the semiconductor wafer at a temperature of 900 C. over a period of 8 h in an atmosphere of nitrogen and a second heat treatment at a temperature of 1100 C. over a period of 2 h in an atmosphere of oxygen and hydrogen. When the mean density of surface defects falls below the value of 1100 cm.sup.2 this is an indication of an inhomogeneous distribution of BMD seeds.
(23) The density of BMDs is not lower than a lower limit of 510.sup.8/cm.sup.3 when determined along the radius R of the semiconductor wafer from a radial position r=R/3 to a radial position r=R/1.15 by IR tomography after heat treatments of the semiconductor wafer at a temperature of 780 C. over a period of 3 h and at a temperature of 1000 C. over a period of 16 h.
(24) To obtain a semiconductor wafer having the recited properties the wafer must originate from a single crystal pulled under certain conditions. During pulling of the single crystal the quotient V/G must remain within narrow limits within which the single crystal crystallizes with an appropriate excess of vacancies in the P.sub.v region. It is preferable when a P.sub.v region with an appropriate excess of vacancies is formed from the center of the single crystal to the edge thereof over a radial length of not less than 98% of the radius of the single crystal. The formation of a P.sub.v region having a comparatively small excess of vacancies must be excluded because in this case too few BMD seeds of sufficient size to withstand the deposition of an epitaxial layer on the semiconductor wafer are formed. However, the excess of vacancies must not be too great either and the radial progression thereof must not vary too much. Thus, the process window for the P.sub.v region must not be fully exploited.
(25) These requirements are fulfilled by controlling the pulling velocity V to control the quotient V/G. In order that the single crystal grows with an appropriate excess of vacancies in the P.sub.v region, the pulling velocity V is controlled with the proviso that the velocity may not take every value in a span V of pulling velocities that ensure growth of the single crystal in the P.sub.v region. The allowed pulling velocity is in a sub range of the span V which comprises 39% of V and whose lowest pulling velocity is 26% greater than the pulling velocity V.sub.Pv/Pi at the transition from the P.sub.v region to the P.sub.i region.
(26) The pulling velocity V.sub.Pv/Pi and the span V are experimentally determined, for example by pulling a test single crystal with linearly increasing or falling progress of the pulling velocity. The same hot zone as is intended for pulling a single crystal according to the invention is used. Every axial position in the test single crystal has a pulling velocity assigned to it. The test single crystal is cut axially and is examined for point defects for example by decoration with copper or by measuring the lifetime of minority charge carriers. The span V extends from the lowest pulling velocity up to the highest pulling velocity at which P.sub.v region can be detected from the center to the edge of the test single crystal over a radial length of not less than 98% of the radius of the test single crystal. The lowest pulling velocity in this context is the pulling velocity V.sub.Pv/Pi.
(27) The pulling velocity V is preferably controlled in the recited fashion in the entire section of the single crystal having a uniform diameter so that all semiconductor wafers cut from this section have the intended properties. The diameter of the single crystal in this section and the diameter of the resulting semiconductor wafers is preferably not less than 200 mm, more preferably not less than 300 mm.
(28) In order to promote the growth of the largest possible proportion of this section of the single crystal over a radial length of not less than 98% of the radius in the P.sub.v region with an appropriate excess of vacancies, it is advantageous to use a hot zone for the pulling of the single crystal on account of which the axial temperature gradient G.sub.c in the center of the crystallization interface is greater in a temperature range from the melting point to 1370 C. than the corresponding temperature gradient G.sub.e at the edge of the crystallization interface. The following preferably applies:
1<G.sub.c/G.sub.e1.15
(29) It is further advantageous to cool the single crystal to impede the formation of defects, for example the formation of seeds of OSF defects. The cooling rates are preferably not lower than:
(30) 1.7 C./min in the temperature range from 1250 C. to 1000 C.;
(31) 1.2 C./min in the temperature range from below 1000 C. to 800 C.; and 0.4 C./min in the temperature range from below 800 C. to 500 C.
(32) It should be borne in mind that due to segregation, the concentration of nitrogen in the single crystal increases from the beginning to the end of the single crystal. In order to obtain the highest possible yields of semiconductor wafers according to the invention it is advantageous to set the axial progression of the concentrations of oxygen and nitrogen in the single crystal counter to one another. Thus the incorporation of oxygen into the single crystal should be controlled such that the initially comparatively low concentration of nitrogen is paired with a comparatively high concentration of oxygen and the concentration of oxygen decreases with increasing concentration of nitrogen. It is preferable when the concentration of oxygen in the section of the single crystal having a uniform diameter at a position 50 mm from the start of this section of the single crystal is not less than 5.410.sup.17 atoms/cm.sup.3.
(33) It is also preferable to set the concentration of hydrogen lower at the start of the section of the single crystal having a uniform diameter than at the end of this section. It is particularly preferable to set the partial pressure of the hydrogen in the atmosphere in which the single crystal is pulled in such a way that the partial pressure is in the range of a lower limit of 5 Pa at the start of the section of the single crystal having a uniform diameter, and is in the range of an upper limit of 15 Pa at the end of this section. For example, in the case of a single crystal of silicon having a diameter of at least 300 mm and a total length of the section having a uniform diameter of at least 2200 mm the partial pressure of hydrogen is set to not less than 5 Pa and not more than 7 Pa as far as half of the total length of the section of the single crystal having a uniform diameter, subsequently increased linearly until in terms of the partial pressure of the hydrogen, is not less than 12 Pa and not more than 15 Pa, and in terms of the length of this section of the single crystal 55% to 60% of the total length thereof have been reached and the partial pressure of the hydrogen is maintained until the section of the single crystal having a uniform diameter has reached the intended total length. This ensures, particularly at the start of the section of the single crystal having a uniform diameter, uniformization of the density of BMDs in the edge region of the subsequently resulting semiconductor wafer and avoids the formation of seeds of OSF defects particularly at the end of this section of the single crystal when the concentration of nitrogen is comparatively high. The limitation of the partial pressure of the hydrogen to the upper limit of 15 Pa moreover reduces the formation of larger BMD seeds from which after deposition of an epitaxial layer on the semiconductor wafer twin dislocations proceed. The presence of twin dislocations makes itself known by an increased number of so-called localized light scatterers (LLS).
(34) A semiconductor wafer according to the invention is separated from a single crystal that has been pulled from a melt under the stated conditions by the CZ method. The upper lateral surface and the lower lateral surface and also the edge of the semiconductor wafer are subsequently subjected to one or more mechanical processing steps and at least one polishing. On the polished upper lateral surface of the semiconductor wafer an epitaxial layer is preferably deposited in a manner known per se. The epitaxial layer is preferably composed of single-crystal silicon and preferably has a thickness of 2 m to 7 m. The temperature during the deposition of the epitaxial layer is preferably 1100 C. to 1150 C. The semiconductor wafer and the epitaxial layer are doped with an electrically active dopant, for example boron, preferably analogously to the doping of a pp.sup.-doped epitaxial semiconductor wafer.
(35) The number of twin dislocations on the surface of the epitaxial layer is preferably less than 5.
(36) The semiconductor wafer having an epitaxial layer obtained by deposition of an epitaxial layer onto the frontside of the semiconductor wafer has the potential, despite the deposition of the epitaxial layer, to be able to form BMDs whose density is sufficient to endow the semiconductor wafer with the necessary activity as an internal getter. However, the density of BMDs remains sufficiently low, and their radial progression sufficiently homogeneous, for problems due to overlay defects to be avoided.
(37) The BMDs are preferably formed in the course of the production of electronic components in the epitaxial layer and attendant heat treatments. However, they can also be formed by subjecting the semiconductor wafer to one or more heat treatments after the deposition of the epitaxial layer and before the production of electronic components.
(38) The density of BMDs in the case of the semiconductor wafer having an epitaxial layer is not less than 310.sup.8/cm.sup.3 and not more than 2.510.sup.9/cm.sup.3 determined from the center to the edge of the semiconductor wafer for an edge exclusion of 1 mm by IR tomography after heat treatments of the semiconductor wafer having an epitaxial layer at a temperature of 780 C. over a period of 3 h and at a temperature of 1000 C. over a period of 16 h.
(39) A further quality attribute of the semiconductor wafer having an epitaxial layer is that the density of BMDs varies by not more than 80% based on a mean density, wherein the density of BMDs along the radius R of the semiconductor wafer having an epitaxial layer is determined from a radial position r=R/1.0791 to a radial position r=R/1.0135 by IR tomography after heat treatments of the semiconductor wafer having an epitaxial layer at a temperature of 780 C. over a period of 3 h and at a temperature of 1000 C. over a period of 16 h. Expressed in another way the following applies:
(D.sub.BMDmaxD.sub.BMDmin)/D.sub.BMDmean0.8
wherein D.sub.BMDmean refers to the density of BMDs meaned along an edge region and D.sub.BMDmax and D.sub.BMDmin refer to the largest and smallest density of BMDs within the edge region and the edge region extends from the radial position r=R/1.0791 to the radial position r=R/1.0135.
(40) Determination of the Hydrogen Concentration:
(41) To determine the hydrogen concentration, an object for measurement in the form of a cuboid block (3 cm3 cm30 cm) is cut from a single crystal. After a heat treatment of the object for measurement at a temperature of 700 C. over a period of 5 min and rapid cooling of the object for measurement the hydrogen concentration is measured by FTIR spectroscopy at room temperature. Before the FTIR measurement a portion of the hydrogen that would otherwise be withdrawn from the measurement is activated by irradiating the object for measurement with gamma rays from a Co.sup.60 source. The energy dose of the radiation is 5000 to 21,000 kGy. A measurement campaign comprises 1000 scans at a resolution of 1 cm.sup.1 per object for measurement. Vibrational bands at wavenumbers of 1832, 1916, 1922, 1935, 1951, 1981, 2054, 2100, 2120 and 2143 cm.sup.1 are evaluated. The concentration of hydrogen is calculated from the sum of the integrated adsorption coefficients of the respective vibrational bands multiplied by the conversion factor 4.41310.sup.16 cm.sup.1. When the hydrogen concentration of a semiconductor wafer is to be measured the heat treatment of the object for measurement at a temperature of 700 C. is eschewed and a strip cut from the semiconductor wafer and having an area of 3 cm20 cm is used as the object for measurement.
(42) Measurement of the Density of BMD Seeds by IR Tomography:
(43) The measurement of the density of BMD seeds by IR tomography (infrared laser scattering tomography) is effected along a radial broken edge of a semiconductor wafer whose crystal lattice is as-grown. In this state the semiconductor wafer has experienced no heat treatment that extinguishes BMD seeds or develops BMD seeds into BMDs. The method of measurement is known per se (Kazuo Moriya et al., J. Appl. Phys. 66, 5267 (1989)). Experimentally determined densities of BMD seeds reported here were determined with an MO-441 BMD-Analyzer measuring instrument from Raytex Corporation.
(44) Measurement of the Density of BMDs by IR Tomography:
(45) Before measurement the semiconductor wafer/the semiconductor wafer having an epitaxial layer is subjected to heat treatments at a temperature of 780 C. over a period of 3 h and at a temperature of 1000 C. over a period of 16 h. The measurement of the density of BMDs is then effected in the same way as in the case of the measurement of the density of BMD seeds.
(46) Measurement of the Density of Surface Defects by Optical Microscopy:
(47) Before measurement the semiconductor wafer is subjected to a first heat treatment at a temperature of 900 C. over a period of 8 h in an atmosphere of nitrogen and subsequently to a second heat treatment at a temperature of 1100 C. over a period of 2 h in an atmosphere of oxygen and hydrogen. An oxide layer that forms on the surface is removed with hydrogen fluoride after the two heat treatments. This is followed by a three minute delineation of surface defects with Secco etchant and counting of the number of surface defects by optical microscopy on the upper lateral surface of the semiconductor wafer along the radius thereof. All surface defects having a longest diagonal greater than 5 m are included in the counting.
(48) The invention is more particularly elucidated hereinbelow having reference to the figures.
(49)
(50)
(51)
(52) For comparison,
(53)
(54) For comparison,
(55)
(56) For comparison,
(57)
(58) The table which follows contains data for semiconductor wafers made of single-crystal silicon with properties in accordance with the invention (examples B1 to B3) and semiconductor wafers which because of failure to meet one or more requirements (comparative examples V1 to V4) are non-inventive semiconductor wafers.
(59) TABLE-US-00001 TABLE BMD seeds.sup.1) Surface BMD density Position.sup.3) [/cm.sup.3] defects.sup.2) [/cm.sup.2] [/cm.sup.3] [mm] B1 1.19 10.sup.6 2974 2.22 10.sup.9 72 B2 1.21 10.sup.6 1430 1.11 10.sup.9 57 B3 2.99 10.sup.5 2208 2.17 10.sup.9 62 V1 2.15 10.sup.6 962 3.90 10.sup.9 87 V2 4.81 10.sup.4 4130 4.88 10.sup.9 97 V3 1.60 10.sup.4 879 3.21 10.sup.8 85 V4 1.93 10.sup.7 1419 7.22 10.sup.8 77 .sup.1)density of the BMD seeds averaged over the radius of the semiconductor wafer; .sup.2)density of the surface defects meaned over the radius; .sup.3)radial position of the minimum of the BMD density.
(60) In contrast to the semiconductor wafers of examples B1 to B3 the semiconductor wafers of comparative examples V1 to V4 failed to meet one or more of the requirements with respect to the density of the BMD seeds, the density of the surface defects and the BMD density. After deposition of an epitaxial layer of silicon only the semiconductor wafers having an epitaxial layer based on the semiconductor wafers of the comparative examples had deficiencies either because of insufficient potential of the internal getter or because of the presence of overlay defects or because of a greater number of twin dislocations.
(61) The semiconductor wafers having an epitaxial layer derived from the semiconductor wafers of examples B1 to B3 did not have such deficiencies.
(62)