We investigated the diffusion behavior of hydrogen in a silicon wafer made by a carbon-cluster ion-implantation technique after heat treatment and silicon epitaxial growth. A hydrogen peak was observed after high-temperature heat treatment (>1000 °C) and silicon epitaxial growth by secondary ion mass spectrometry analysis. We also confirmed that the hydrogen peak concentration decreased after epitaxial growth upon additional heat treatment. Such a hydrogen diffusion behavior has not been reported. Thus, we derived the activation energy from the projected range of a carbon cluster, assuming only a dissociation reaction, and obtained an activation energy of 0.76 ± 0.04 eV. This value is extremely close to that for the diffusion of hydrogen molecules located at the tetrahedral interstitial site and hydrogen molecules dissociated from multivacancies. Therefore, we assume that the hydrogen in the carbon-cluster projected range diffuses in the molecular state, and hydrogen remaining in the projected range forms complexes of carbon, oxygen, and vacancies.

REGULAR PAPERS • OPEN ACCESSEffect of dose and size on defect engineering in carbon cluster implanted silicon wafers Carbon-cluster-ion-implanted defects were investigated by high-resolution cross-sectional transmission electron microscopy toward achieving high-performance CMOS image sensors. We revealed that implantation damage formation in the silicon wafer bulk significantly differs between carbon-cluster and monomer ions after implantation. After epitaxial growth, small and large defects were observed in the implanted region of carbon clusters. The electron diffraction pattern of both small and large defects exhibits that from bulk crystalline silicon in the implanted region. On the one hand, we assumed that the silicon carbide structure was not formed in the implanted region, and small defects formed because of the complex of carbon and interstitial silicon. On the other hand, large defects were hypothesized to originate from the recrystallization of the amorphous layer formed by high-dose carbon-cluster implantation. These defects are considered to contribute to the powerful gettering capability required for high-performance CMOS image sensors.

We developed silicon epitaxial wafers with high gettering capability by using hydrocarbon–molecular–ion implantation. These wafers also have the effect of hydrogen passivation on process-induced defects and a barrier to out-diffusion of oxygen of the Czochralski silicon (CZ) substrate bulk during Complementary metal-oxide-semiconductor (CMOS) device fabrication processes. We evaluated the electrical device performance of CMOS image sensor fabricated on this type of wafer by using dark current spectroscopy. We found fewer white spot defects compared with those of intrinsic gettering (IG) silicon wafers. We believe that these hydrocarbon–molecular–ion–implanted silicon epitaxial wafers will improve the device performance of CMOS image sensors.

The effect of oxygen (O) concentration on the Fe gettering capability in a carbon-cluster (C 3 H 5 ) ion-implanted region was investigated by comparing a Czochralski (CZ)-grown silicon substrate and an epitaxial growth layer. A high Fe gettering efficiency in a carbon-cluster ion-implanted epitaxial growth layer, which has a low oxygen region, was observed by deep-level transient spectroscopy (DLTS) and secondary ion mass spectroscopy (SIMS). It was demonstrated that the amount of gettered Fe in the epitaxial growth layer is approximately two times higher than that in the CZ-grown silicon substrate. Furthermore, by measuring the cathodeluminescence, the number of intrinsic point defects induced by carboncluster ion implantation was found to differ between the CZ-grown silicon substrate and the epitaxial growth layer. It is suggested that Fe gettering by carbon-cluster ion implantation comes through point defect clusters, and that O in the carbon-cluster ion-implanted region affects the formation of gettering sinks for Fe.

We investigated the fundamental characteristics of a CH3O-ion-implanted silicon epitaxial wafer with our previously developed multielement molecular ion implantation technique and compared this technique with a conventional implantation technique, i.e., “carbon cluster ion implantation”. We found that the CH3O ion projection range has a 10-fold higher oxygen concentration than the carbon cluster ion projection range after epitaxial growth. We also found 50 nm silicon {111} stacking faults in the CH3O ion projection range. Such defects were not observed in the carbon cluster ion projection range. From nickel gettering test results, proximity gettering of nickel contaminations by CH3O ion implantation was found to be more effective than that by C2H3 ion implantation. Therefore, we speculate that the CH3O ion projection range improves the gettering capability of metallic impurity contaminants through the formation of complex point defects formed by vacancies and that oxygen implanted at a high concentration and silicon {111} stacking faults are new gettering sinks.